Resin film and manufacturing method for the same, and resin laminated metal sheet using said resin film and manufacturing method for the same

ABSTRACT

A resin film of a two-layer-construction comprising: (a) a resin layer R1 including a non-stretched resin film which contains a thermoplastic polyester resin containing 3 to 30 percent by weight in a weight fraction in the entire resin of a granular resin with a grain diameter of 0.1 to 5 μm, the granular resin being a modified polyolefin resin containing 2 to 20 percent by weight of a functional group derived from carboxylic acid in terms of carboxylic acid, and (b) a polyester resin layer R0 containing at least one of polyethylene terephthalate and isophthalic acid copolymerized polyethylene terephthalate, as a basic skeleton, wherein the resin layer R1 and the resin layer R2 are laminated to each other.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of application Ser. No.10/665,459 filed Sep. 18, 2003 (U.S. Pat. No. 7,063,889), which is acontinuation application of International Application PCT/JP02/12222filed Nov. 22, 2002.

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention relates to a resin film for a resin laminatedmetal sheet, more particularly, a resin film having high formability,impact resistance, adhesion, flavor property, and retort resistance, anda manufacturing method for the same, and a resin laminated metal sheetusing the resin film and a manufacturing method for the same.

2. Background Art

Conventionally, as a metallic can that is subjected to severe forming,such as a thin-wall deep drawn can or a drawn and ironed can (DI can), acan provided with a resin layer on the internal surface thereof isgenerally used to prevent a decrease in taste and flavor and hence achange in property of the content due to dissolution of metal from ametal sheet. As such a can that is provided with a resin layer on theinternal surface thereof and a resin-coated metal sheet capable offorming such a can, a metal sheet to which polyester resin is laminatedis used as a substitute for epoxy coating layer of which danger ofendocrine disrupter has recently been pointed out.

The polyester resin used in such an application is required to providethe following performance: The adhesion to a metal sheet is good, sothat deformation such as elongation and compression of film caused byforming at the can manufacturing time and deterioration of film anddecrease in adhesion due to friction do not occur; a polyester resinfilm is not crystallized or deteriorated after heat treatment such asdrying, printing, and retorting, and hence-separation and shrinkage offilm, cracks, pinholes, etc. do not occur; a polyester film is notcracked or separated by a impact to a can; corrosion or peeling does notoccur when polyester resin comes into contact with various kinds ofcontents; a film is not whitened; and so on. Furthermore, it is requiredthat flavor components of content in a can be not adsorbed or absorbedto a polyester film, or the flavor of content be not impaired by thedissolved components of polyester film and smell (hereinafter referredto as flavor property).

For example, in Unexamined Japanese Patent Publication No. 59-232852, ametal sheet coated with polyethylene terephthalate resin is proposedfrom a viewpoint of formability, heat resistance, corrosion resistance,flavor property, etc. Also, in Unexamined Japanese Patent PublicationNo. 1-180336, a metal sheet coated with polybutylene terephthalate resinis proposed. Furthermore, excellent formability that withstands drawingand ironing is required, and also excellent adhesion such that a resinfilm does not separate from a steel sheet and impact resistance such asto withstand shocks at the can manufacturing time, the canning time, andtransportation time are required. To meet the requirements, UnexaminedJapanese Patent Publication Nos. 5-269920 and 6-320669 have disclosed amanufacturing method in which excellent formability, adhesion, andimpact resistance can be obtained in addition to food sanitationproperty and flavor property, which a polyethylene terephthalate resinfilm inherently has, by controlling the crystalline orientation of filmby means of laminating technology or the like. Such a technology can beapplied to the present requirement level for formability, adhesion, andimpact resistance.

However, in the concerned field, the decrease in sheet thickness isprogressing year by year, and this tendency is thought to continue inthe future as well. In the above-described manufacturing method forpolyethylene terephthalate resin, it is difficult to achieve bothformability and impact resistance when the resin film is subjected toseverer forming. The reason for this is that formability and impactresistance depend greatly on the crystalline orientation (planeorientation), and have a mutually contradictory tendency. Specifically,if a crystalline orientation component increases in a resin layer,plastic deformation is hindered by a crystalline portion, and henceformability is deteriorated. Therefore, from the viewpoint offormability, the smaller amount of oriented crystals is, the betterformability is. However, since this crystalline portion acts as aportion for stopping the progress of crack, from the viewpoint of impactresistance, the larger amount of oriented crystals is, the higher impactresistance is. Thus, formability and impact resistance are designed byregulating the amount of oriented crystals so that both properties arein the allowable region. However, the region in which both propertiesare compatible is the present limit of required performance, so that ithas been expected that a new highly formable film that can respond to anincrease in the degree of forming in the future, and a resin laminatedmetal sheet coated with this film will be developed.

In order to satisfy such a need, studies have been conducted earnestlyon a technology in which both high formability and impact resistance areachieved by mixing polyolefin resin with polyester resin. UnexaminedJapanese Patent Publication Nos. 7-195617 and 7-195618 have disclosed atechnology in which a film consisting of a composition of saturatedpolyester resin and ionomer resin is laminated to a metal sheet.Although these publications indicate that impact resistance can be kepteven in an amorphous state, the impact resistance obtained merely byaddition of ionomer is insufficient, and inversely, the orientation ofpolyester resin is actually hindered by the addition of ionomer, whichposes a problem in that the mechanical strength that polyester resininherently has decreases, and resin is broken at the forming time. Also,the adhesion to a substrate metal after forming or after heating is alsoinferior.

Furthermore, Japanese Patent Publication Nos. 7-290643 and 7-290644 havedisclosed that impact resistance can be improved by laminating a ternarycomposition of polyester resin, polyester elastomer, and ionomer resinto a metal sheet. However, the mixture of this composition also has lowcapability for relaxing impact stress of polyester elastomer, so thatthe effect of improving impact resistance of polyester resin is verylittle. Also, as in the case where elastomer is not added, the adhesionto a substrate metal after forming or after heating is also inferior.

On the other hand, WO 99/27026 Publication has disclosed a technology inwhich an elastomer resin encapsulated by a vinyl polymer having a polargroup is finely dispersed in polyester resin. Such fine dispersion ofelastomer resin improves impact resistance, so that the level offormability and impact resistance is high. However, the control ofprocess for manufacturing such a capsule state is difficult to carryout, and the dispersed state of elastomer resin changes greatlydepending on the resin forming conditions, and is unstable. Therefore,there arises a problem in that the performance of the resultantlyobtained resin film is not always constant. It is found that if such adispersed state deviates from the optimum conditions, the performancedecreases greatly. Even if a resin of such a composition is actuallymanufactured, a portion where the resin performance is low is producedpartially, so that the obtained performance such as formability andimpact resistance is insufficient as a whole. Furthermore, there ariseproblems of decreased adhesion to a substrate metal due to forming orimpact and decreased adhesion after heating.

Furthermore, Unexamined Japanese Patent Publication No. 2001-172481 hasdisclosed a technology in which the decomposition of vinyl polymer isrestrained by adding an appropriate amount of an oxidation inhibitor(free radical inhibitor) to a mixed resin in which a vinyl polymerhaving a polar group is finely dispersed in polyester resin. However, ina particular mixture of vinyl polymer and polyester resin, when apolymerization catalyst of polyester resin and an oxidation inhibitorcoexist, resin is liable to be deteriorated. In particular, polyesterresin is deteriorated, and performance such as impact resistance andflavor property is decreased.

Still further, Unexamined Japanese Patent Publication No. 2001-353814has disclosed a technology in which a resin layer in which fine ionomerresin exists in polyester resin as a dispersion phase is coated, bywhich the impact resistance and adhesion are enhanced. However, thecompositions of dispersed modified polyolefin resin and polyester resinare improper, so that the performance is insufficient.

Also, a can using a metal sheet to which such a resin film is laminatedhas a problem in that the film is whitened after retorting and therebythe appearance is deteriorated. In particular, a can lid and a canbottom, which come-into direct contact with retort steam, remarkably iswhitened, and such a phenomenon cannot be prevented by means of theabove-described prior art.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a resin film havinghigh formability, impact resistance, adhesion, flavor property, andretort resistance, and a manufacturing method for the same, and a resinlaminated metal sheet using the resin film and a manufacturing methodfor the same.

The inventors carried out studies on the construction of resin layerthat withstands severer forming and keeps performance such as impactresistance and adhesion without losing advantages of high formabilityand flavor property that polyester resin inherently has. Further, wepursued a resin composition by which that construction can be obtainedstably regardless of the forming conditions. As a result, we found thata metal sheet coated with a resin film consisting of a mixed resin inwhich granular modified polyolefin resin having a specific compositionis dispersed in polyester resin provides dramatically high formability,impact resistance, and flavor property, and also has adhesion afterforming and after heating. Moreover, this resin construction can beobtained stably regardless of the forming conditions. Further, it wasverified that in this resin composition, necessary characteristics suchas corrosion resistance are also sufficient.

The optimum resin construction of mixed resin layer can be obtained whengranular modified polyolefin resin containing a specific amount of afunctional group derived from carboxylic acid is dispersed in polyesterresin. The modified polyolefin resin having such a functional groupcomposition is dispersed in polyester resin most stably, and moreoverthe mechanical properties of the modified polyolefin resin itself areoptimal, so that high formability and impact resistance can be provided.

As the reason that both formability and impact-resistance can beachieved, the following mechanism is presumed. When a destructive forceacts on resin by means of severe forming or impact, a craze or crack isgenerated in polyester resin, and grows, resulting in breakage. However,if granular modified polyolefin resin having a proper composition andgrain size is dispersed in polyester resin, the progress of such a crazeor crack is restrained by stress relaxation of modified polyolefinresin, so that final occurrence of breakage can be prevented. Further,there appears an effect that the plastic deformation of polyester resinis accelerated in the surroundings in which modified polyolefin resin isin contact with polyester resin, and hence stress concentration thatresults in breakage is relaxed, and the resin is less liable to bebroken.

A resin film obtained by mixing modified polyolefin resin containingcarboxylic acid with polyester resin has higher adhesion to a substratemetal than the ordinary polyester resin, but may have insufficientadhesion when being subjected to severer forming. Also, a film havingsuch a resin composition exhibits high formability and impactresistance, and also exhibits flavor property high enough to ordinaryuse. However, it is true that many persons are very sensitive to achange in flavor depending on the recent applications, and impose veryrigid requirements. Contrary to such requirements, polyester resin inwhich modified olefin is dispersed may have an insufficient flavorproperty because it contains an olefin compound.

Thereupon, as the result of earnest studies, it was found that a layerof modified polyolefin resin containing carboxylic acid is made a layerthat is in contact with a metal sheet, by which adhesion after formingand after heating is improved dramatically. Further, this modifiedpolyolefin resin layer has high adhesion to mixed resin layer, so thatthere occurs no separation between layers, and thus high adhesion can bekept as a whole. Also, it was found that by lapping a polyester resinlayer containing no polyolefin resin on a modified olefin dispersedpolyester resin, the flavor property can be enhanced to a level higherthan the required one.

The present invention has been made based on the above-describedknowledge, and the gist thereof is as described below.

(1) A resin film consisting of a mixed resin in which a granular resinmainly existing in a granular state in which the grain diameter is 0.1to 5 μm is dispersed in thermoplastic polyester resin in the range of 3to 30% by weight in weight fraction in entire resin, characterized inthat the granular resin is modified polyolefin resin containing 2 to 20%by weight of a functional group derived from carboxylic acid in terms ofcarboxylic acid.

(2) The resin film described in item (1), characterized in that theamount of the modified polyolefin resin existing in a film in a granularstate in which the grain diameter is 0.1 to 5 μm is in the range of 3 to25% by volume in volume fraction in entire resin.

(3) The resin film described in item (1) or (2), characterized in thatthe thermoplastic polyester resin is polyester containing polyethyleneterephthalate and/or isophthalic acid copolymerized polyethyleneterephthalate as a main basic skeleton.

(4) The resin film described in any one of items (1) to (3),characterized in that the ratio of terephthalic acid to isophthalicacid, which are dicarboxylic acid components constituting thethermoplastic polyester resin, is 97:3 to 85:15 in molar ratio.

(5) The resin film described in any one of items (1) to (4),characterized in that in a monomer component mainly constituting thethermoplastic polyester resin, dicarboxylic acid is terephthalic acid,and diol components are ethylene glycol and 1,4-butanediol, the ratiothereof being 20:80 to 80:20 in molar ratio.

(6) The resin film described in any one of items (1) to (5),characterized in that the ratio X/Y of the amount X of polyesterpolymerization catalyst to the amount Y of oxidation inhibitor in themixed resin is 0.2 or higher in weight ratio.

(7) The resin film described in any one of items (1) to (6),characterized in that the content of oxidation inhibitor in the mixedresin is 500 ppm or lower.

(8) The resin film described in any one of items (1) to (7),characterized in that the resin film contains 5 to 40% by weight ofpigment.

(9) The resin film described in any one of items (1) to (7),characterized in that the resin film has a thickness of 10 to 50 μm.

(10) A resin film having a construction in which a resin layer of R1layer consisting of the mixed resin described in any one of items (1) to(8) and a polyester resin layer of R0 layer containing polyethyleneterephthalate and/or isophthalic acid copolymerized polyethyleneterephthalate as a main basic skeleton are laminated, characterized inthat the film is designed so that when it is laminated to a metal sheet,the R0 layer is the outermost layer.

(11) The resin film described in item (10), characterized in that thefilm thickness of the R1 layer is 10 to 50 μm, the film thickness of theR0 layer is 1 to 10 μm, and the thickness ratio R1/R0 of the R1 layer tothe R0 layer is 2/1 to 10/1.

(12) A resin film having a construction in which a resin layer of R1layer consisting of the mixed resin described in any one of items (1) to(8) and a resin layer of R2 layer consisting mainly of modifiedpolyolefin resin having a functional group derived from carboxylic acidare laminated, characterized in that the film is designed so that whenit is laminated to a metal sheet, the R2 layer is in contact with themetal sheet.

(13) The resin film described in item (12), characterized in that thefilm thickness of the R1 layer is 10 to 50 μm, the film thickness of theR2 layer is 1 to 10 μm, and the thickness ratio R1/R2 of the R1 layer tothe R2 layer is 1/1 to 20/1.

(14) A resin film having a three-layer construction of R0 layer/R1layer/R2 layer in which a polyester resin layer of R0 layer containingpolyethylene terephthalate and/or isophthalic acid copolymerizedpolyethylene terephthalate as a main basic skeleton is laminated on onesurface of a resin layer of R1 layer consisting of the mixed resindescribed in any one of items (1) to (8), and a resin layer of R2 layerconsisting mainly of modified polyolefin resin having a functional groupderived from carboxylic acid is laminated on the other surface of the R1layer, characterized in that the film is designed so that when it islaminated to a metal sheet, the R0 layer is the outermost layer.

(15) The resin film described in item (14), characterized in that thefilm thickness of the R1 layer is 10 to 50 μm, the film thickness of theR0 layer is 1 to 10 μm, the film thickness of the R2 layer is 1 to 10μm, the thickness ratio R1/R0 of the R1 layer to the R0 layer is 2/1 to10/1, and the thickness ratio R1/R2 of the R1 layer to the R2 layer is1/1 to 20/1.

(16) The resin film described in any one of items (12) to (15),characterized in that the modified polyolefin resin of the R2 layercontains 2 to 20% by weight of a functional group derived fromcarboxylic acid in terms of carboxylic acid.

(17) The resin film described in any one of items (10) to (16),characterized in that the resin film contains 5 to 40% by weight ofpigment.

(18) A manufacturing method for a resin film, characterized in that inmanufacturing the resin film described in any one of items (1) to (9),the mixed resin in which a granular modified polyolefin resin with agrain diameter of 0.1 to 5 μm is dispersed in advance in thermoplasticpolyester resin described in any one of items (1) to (8) is inserted inan extruding machine as a raw material resin and is melted, and a filmis formed by extruding the molten resin from a T die.

(19) A manufacturing method for a resin film, characterized in that inmanufacturing the resin film described in item (10), (11) or (17), themixed resin in which a granular modified polyolefin resin with a graindiameter of 0.1 to 5 μm is dispersed in advance in thermoplasticpolyester resin described in any one of items (1) to (8) is inserted inan extruding machine as a raw material resin for the R1 layer and ismelted; at the same time, polyester resin containing polyethyleneterephthalate and/or isophthalic acid copolymerized polyethyleneterephthalate as a main basic skeleton is inserted in a separateextruding machine as a raw material resin for the R0 layer and ismelted; and a film of two-layer construction of R1 layer/R0 layer isformed by extruding the molten resins from one T die.

(20) A manufacturing method for a resin film, characterized in that inmanufacturing the resin film described in item (12), (13), (16) or (17),the mixed resin in which a granular modified polyolefin resin with agrain diameter of 0.1 to 5 μm is dispersed in advance in thermoplasticpolyester resin described in any one of items (1) to (8) is inserted inan extruding machine as a raw material resin for the R1 layer and ismelted; at the same time, a resin consisting mainly of modifiedpolyolefin resin having a functional group derived from carboxylic acidis inserted in a separate extruding machine as a raw material resin forthe R2 layer and is melted; and a film of two-layer construction of R1layer/R2 layer is formed by extruding the molten resins from one T die.

(21) A manufacturing method for a resin film, characterized in that inmanufacturing the resin film described in items (14) to (17), the mixedresin in which a granular modified polyolefin resin with a graindiameter of 0.1 to 5 μm is dispersed in advance in thermoplasticpolyester resin described in any one of items (1) to (8) is inserted inan extruding machine as a raw material resin for the R1 layer and ismelted; at the same time, polyester resin containing polyethyleneterephthalate and/or isophthalic acid copolymerized polyethyleneterephthalate as a main basic skeleton is inserted in a separateextruding machine as a raw material resin for the R0 layer and ismelted, and also a resin consisting mainly of modified polyolefin resinhaving a functional group derived from carboxylic acid is inserted inanother separate extruding machine as a raw material resin for the R2layer and is melted; and a film of three-layer construction of R0layer/R1 layer/R2 layer is formed by extruding the molten resins fromone T die.

(22) A resin laminated metal sheet characterized in that at least onesurface of a metal sheet is coated with the resin film described in anyone of items (1) to (17) or the resin film manufactured by the methoddescribed in any one of items (18) to (21).

(23) The resin laminated metal sheet described in item (22),characterized in that the metal sheet is a steel sheet subjected toelectrolytic chromate treatment, having a metallic chromium layer of 50to 200 mg/m² and a chromium oxide layer of 3 to 30 mg/m² in terms ofmetallic chromium on the surface thereof.

(24) The resin laminated metal sheet described in item (22) or (23),characterized in that a plane orientation coefficient in the directionparallel to the film surface of the resin film is lower than 0.010.

(25) The resin laminated metal sheet described in any one of items (22)to (24), characterized in that the surface of metal sheet is coated withthe resin film by an extrusion laminating method in which the mixedresin described in any one of items (1) to (8) is extruded from a T diedirectly on the surface of metal sheet.

(26) The resin laminated metal sheet described in any one of items (22)to (24), characterized in that the surface of metal sheet is coated withthe resin film by a two-layer extrusion laminating method in which twotypes of resins consisting of a resin layer (R1 layer) consisting of themixed resin described in any one of items (1) to (8) and a resin layer(R0 layer) consisting of polyester resin containing polyethyleneterephthalate and/or isophthalic acid copolymerizedpolyethylene-terephthalate as a main basic skeleton are extrudedsimultaneously from one T die directly on the surface of metal sheet.

(27) The resin laminated metal sheet described in any one of items (22)to (24), characterized in that the surface of metal sheet is coated withthe resin film by a two-layer extrusion laminating method in which twotypes of resins consisting of a resin layer (R1 layer) consisting of themixed resin described in any one of items (1) to (8) and a resin layerof R2 layer consisting mainly of modified polyolefin resin having afunctional group derived from carboxylic acid are extrudedsimultaneously from one T die directly on the surface of metal sheet.

(28) The resin laminated metal sheet described in any one of items (22)to (24), characterized in that the surface of metal sheet is coated withthe resin film by a three-layer extrusion laminating method in whichthree types of resins consisting of a resin layer (R0 layer) consistingof polyester resin containing polyethylene terephthalate and/orisophthalic acid copolymerized polyethylene terephthalate as a mainbasic skeleton, a resin layer (R1 layer) consisting of the mixed resindescribed in any one of items (1) to (8), and a resin layer of R2 layerconsisting mainly of modified polyolefin resin having a functional groupderived from carboxylic acid are extruded simultaneously from one T diedirectly on the surface of metal sheet.

(29) A manufacturing method for a resin laminated metal sheet,characterized in that in manufacturing the resin laminated metal sheetdescribed in any one of items (22) to (28), a resin film is laminated toa metal sheet heated to a temperature in the range of the melting pointof polyester resin in the mixed resin described in any one of items (1)to (8) minus 70° C. to the melting point thereof plus 30° C.

(30) A manufacturing method for a resin laminated metal sheet,characterized in that in manufacturing the resin laminated metal sheetdescribed in item (25), after the mixed resin is heated to a temperaturein the range of the melting point of polyester resin in the mixed resinplus 10° C. to the melting point thereof plus 50° C. and is melted, themolten resin is extruded directly on the surface of metal sheet and islaminated thereon.

(31) The manufacturing method for a resin laminated metal sheetdescribed in item (30), characterized in that after the mixed resin inwhich granular modified polyolefin resin with a grain diameter of 0.1 to5 μm is dispersed in advance in thermoplastic polyester resin describedin any one of items (1) to (8) is inserted in an extruding machine as araw material resin and is melted, the molten resin is extruded directlyon the surface of metal sheet and is laminated thereon.

(32) A manufacturing method for a resin laminated metal sheet,characterized in that in manufacturing the resin laminated metal sheetdescribed in item (26), after the R1 and R0 layers are heated to atemperature in the range of the melting point of polyester resin in theR1 layer plus lot to the melting point thereof plus 50° C. and aremelted, the molten resins are extruded in two layers on the surface ofmetal sheet and are laminated thereon.

(33) The manufacturing method for a resin laminated metal sheetdescribed in item (32), characterized in that the mixed resin in whichgranular modified polyolefin resin with a grain diameter of 0.1 to 5 μmis dispersed in advance in thermoplastic polyester resin described inany one of items (1) to (8) is inserted in an extruding machine as a rawmaterial resin for the R1 layer; at the same time, a resin consisting ofpolyester resin containing polyethylene terephthalate and/or isophthalicacid copolymerized polyethylene terephthalate as a main basic skeletonis inserted in a separate extruding machine as a raw material resin forthe R0 layer; and then, after these resins are melted, the molten resinsare extruded on the surface of metal sheet and are laminated thereon.

(34) A manufacturing method for a resin laminated metal sheet,characterized in that in manufacturing the resin laminated metal sheetdescribed in item (27), after the R1 and R2 layers are heated to atemperature in the range of the melting point of polyester resin in theR1 layer plus 10° C. to the melting point thereof plus 50° C. and aremelted, the molten resins are extruded in two layers on the surface ofmetal sheet and are laminated thereon.

(35) The manufacturing method for a resin laminated metal sheetdescribed in item (34), characterized in that the mixed resin in whichgranular modified polyolefin resin with a grain diameter of 0.1 to 5 μmis dispersed in advance in thermoplastic polyester resin described inany one of items (1) to (8) is inserted in an extruding machine as a rawmaterial resin for the R1 layer; at the same time, a resin consistingmainly of modified polyolefin resin having a functional group derivedfrom carboxylic acid is inserted in a separate extruding machine as araw material resin for the R2 layer; and then, after these resins aremelted, the molten resins are extruded on the surface of metal sheet andare laminated thereon.

(36) A manufacturing method for a resin laminated metal sheet,characterized in that in manufacturing the resin laminated metal sheetdescribed in item (28), after the R1, R2 and R0 layers are heated to atemperature in the range of the melting point of polyester resin in theR1 layer plus 10° C. to the melting point thereof plus 50° C. and aremelted, the molten resins are extrusion laminated in three layers on thesurface of metal sheet.

(37) The manufacturing method for a resin laminated metal sheetdescribed in item (36), characterized in that the mixed resin in whichgranular modified polyolefin resin with a grain diameter of 0.1 to 5 μmis dispersed in advance in thermoplastic polyester resin described inany one of items (1) to (8) is inserted in an extruding machine as a rawmaterial resin for the R1 layer; at the same time, polyester resincontaining polyethylene terephthalate and/or isophthalic acidcopolymerized polyethylene terephthalate as a main basic skeleton isinserted in a separate extruding machine as a raw material resin for theR0 layer, and also a resin consisting mainly of modified polyolefinresin having a functional group derived from carboxylic acid is insertedin another separate extruding machine as a raw material resin for the R2layer; and then, after these resins are melted, the molten resins areextruded on the surface of metal sheet and are laminated thereon.

DETAILED DESCRIPTION OF THE INVENTION

A resin film in accordance with the present invention and amanufacturing method for the same, and a resin laminated metal sheetusing the resin film and a manufacturing method for the same aredescribed below.

The resin film in accordance with the present invention consists of amixed resin in which a granular resin mainly existing in a state ofgrain with a diameter of 0.1 to 5 μm is dispersed in thermoplasticpolyester resin in the range of 3 to 30% by weight of entire resin, thegranular resin being modified polyolefin resin having a functional groupderived from carboxylic acid.

Specifically, the resin film in accordance with the present invention isformed mainly of thermoplastic polyester resin. The used thermoplasticpolyester resin is such that as the acid component, various kinds ofaromatic dicarboxylic acids and aliphatic-dicarboxylic acids arecopolymerized arbitrarily, and as the glycol component, various kinds ofaliphatic diols and aromatic diols are copolymerized arbitrarily.

As the acid component, concretely, terephthalic acid, phthalic acid,isophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, diphenic acid,diphenyl ether carboxylic acid, 5-sulfoisophthalic acid, diphenoxyethane dicarboxylic acid, adipic acid, oxalic acid, malonic acid,succinic acid, malic acid, citric acid, glutaric acid, dimer acid,pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecadion acid,trans-1,4-cyclohexane dicarboxylic acid, or the like is used. Inparticular, the acid component that is formed mainly of tereophthalicacid and/or isophthalic acid is suitable in terms of the balance ofmechanical properties, flavor property, etc.

On the other hand, as the glycol component, concretely, ethylene glycol,propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol,neopentyl glycol, pentamethylene glycol, hexamethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol,polyethylene glycol, trans-1,4-cyclohexanedimethanol, bisphenols,p-xylene glycol, cis-1,4-cyclohexanedimethanol, hydroquinone,2,2-bis(4-β-hydroxyethoxyphenyl) propane, hydrogenated bisphenol A, orthe like is used. In particular, the glycol component that is formedmainly of ethylene glycol and/or 1,4-butanediol is suitable in terms ofthe balance of mechanical properties, flavor property, etc.

That is to say, thermoplastic polyester resin formed mainly oftereophthalic acid and ethylene glycol, and/or one formed mainly oftereophthalic acid and isophthalic acid and ethylene glycol, and/or oneformed mainly of tereophthalic acid and ethylene glycol and1,4-butanediol are especially suitable in terms of the balance ofmechanical properties and flavor property in a mixed-resin state.

As thermoplastic polyester resin, polyester resin containingpolyethylene terephthalate and/or isophthalic acid copolymerizedpolyethylene terephthalate as a main basic skeleton is suitable. Thepolyester resin containing polyethylene terephthalate and/or isophthalicacid copolymerized polyethylene terephthalate as a main basic skeletonmeans polyester resin in which the sum of a portion in which onlyethylene glycol and tereophthalic acid in the polyester resin skeletonare a unit and/or a portion in which ethylene glycol and tereophthalicacid and isophthalic acid are a unit accounts for 90% or more by weight.In other portions, as the acid component, various kinds of aromaticdicarboxylic acids and aliphatic dicarboxylic acids may be copolymerizedarbitrarily.

Furthermore, in the scope in which the object of the present inventionis not impaired, a unit derived from a polyfunctional compound such astrimesic acid, pyromellitic acid, trimethylolethane, trimethylolpropane,trimethylolmethane, and pentaerythritol may be contained in a smallamount, for example, 2% or less by weight.

For the polyester resin in accordance with the present invention, thecontent of diethylene glycol is preferably 1.5% or lower by weight,further preferably 0.9% or lower by weight. If the content of diethyleneglycol is high, deterioration of polymer progresses due to heatingtreatment such as drying and printing at the forming time, and hencecracks or pinholes are produced, so that the impact resistance andflavor property are sometimes deteriorated.

Also, the content of acetaldehyde in resin is preferably 10 ppm orlower, further preferably 7 ppm or lower, from the viewpoint of flavorproperty. If the content of acetaldehyde exceeds this range, especially10 ppm, the flavor property is sometimes deteriorated. The method forlimiting the content of acetaldehyde to 10 ppm or lower is not subjectto any special restriction. For example, a method can be cited in whichpolyester resin is formed into a film, the polyester resin beingobtained by a method in which resin is heat-treated at a temperaturebelow the melting point of polyester under a reduced pressure or in aninert gas atmosphere to remove acetaldehyde produced by thermaldecomposition at the time when polyester resin is manufactured bycondensation polymerization etc. Preferably, a method should be used inwhich polyester resin that is obtained by solid-phase polymerizing resinat a temperature higher than 150° C. and lower than the melting pointunder a reduced pressure or in an inert gas atmosphere.

Also, the polyester resin in accordance with the present inventionpreferably has less oligomer consisting of a cyclic trimer etc. in resinfrom the viewpoint of flavor property. In particular, the content ofcyclic trimer is preferably 0.9% or less by weight, further preferably0.7% or less by weight. If the content of oligomer in resin exceeds thisrange, especially 0.9% by weight, the flavor property is sometimesdeteriorated. The method for limiting the content of oligomer to 0.9% orless by weight is not subject to any special restriction, and thiscontent of oligomer can be achieved by using the same method as theabove-described method for reducing the content of acetaldehyde.

The intrinsic viscosity of polyester resin used in the present inventionis preferably 0.3 to 2.0 dl/g, further preferably 0.3 to 1.5 dl/g, stillfurther preferably 0.5 to 1.0 dl/g. If the intrinsic viscosity exceeds2.0 dl/g, the mixing with modified polyolefin resin is remarkablydifficult to do because of very high viscosity. As the result ofnonuniform dispersion of modified polyolefin resin, the mechanicalstrength and impact resistance of polyester resin may be decreased. Onthe other hand, if the intrinsic viscosity is lower than 0.3 dl/g, theformability is poor because of low viscosity, so that it may becomedifficult to manufacture a uniform film. The intrinsic viscosity ismeasured by the method specified in JIS K7367-5. It is measured ino-chlorophenol at 25° C. in a concentration of 0.005 g/ml, and isdetermined by the formula of intrinsic viscosity=(T−T₀)/(T₀×c). In thisformula, c expresses resin concentration-per 100 ml of solution in gram,and T and T₀ express drop time in a capillary viscometer of solvent andresin solution, respectively.

Further, the glass-transition temperature (Tg) of the polyester resinused in the present invention is preferably 50 to 120° C., furtherpreferably 60 to 100° C. If the glass-transition temperature is lowerthan 50° C., a flaw etc. are liable to be produced by a temperature riseat the forming time because of deteriorated heat resistance of polyesterresin. On the other hand, if the glass-transition temperature exceeds120° C., inversely the formability is sometimes deteriorated. Also, thelow-temperature crystallization temperature (Tc) is usually 130 to 210°C., preferably 140 to 200° C. The melting point (Tm) is usually 210 to265° C., preferably 220 to 260° C. If the low-temperaturecrystallization temperature is lower than 130° C., crystallization isliable to occur, so that crystallization occurs at the time of retorting(high-temperature high-humidity treatment at about 120° C. In thisdescription, referred also to as “retorting”), by which the film iseasily cracked or separated. On the other hand, if the low-temperaturecrystallization temperature exceeds 210° C., the formability andmechanical strength such as impact resistance of polyester may bedeteriorated. If the melting point is lower than 210° C., resin isdeteriorated by heat at the forming time, so that cracks or pinholes areliable to be produced. On the other hand, if the melting point exceeds265° C., crystallization progresses due to heating treatment such asdrying and printing at the forming time, and hence cracks or pinholesare also liable to be produced. The above-described glass-transitiontemperature, low-temperature crystallization temperature, and crystalmelting point are obtained by measuring endothermic peak temperature atthe time of temperature rise using a differential scanning calorimeter(DSC). The measurement is made under conditions of a sample amount of 10mg and a temperature rise rate of 10° C./min.

In the present invention, in a dicarboxylic acid component constitutingpolyester resin, the ratio of total amount of terephthalic acid to thetotal amount of isophthalic acid is specified so as to be 97:3 to 85:15in molar ratio. In the mixed resin in the present invention, modifiedpolyolefin in resin hinders crystallization of polyester resin, so thatthe decrease in adhesion and corrosion resistance caused by forming,heating, etc. is less liable to occur. Therefore, the optimum ratiospreads toward the terephthalic acid rich side as compared with the casewhere modified polyolefin resin is not contained. Thus, even ifhomo-ethylene terephthalate resin that does not contain isophthalic acidat all is used as polyester resin, when the polyester resin containsmodified polyolefin resin of the present invention, it can be used as anordinary can material. Further, if 3 mol % of isophthalic acid iscopolymerized, the adhesion after forming and heating increasesdramatically. If the amount of isophthalic acid increases as comparedwith the ratio of total amount of terephthalic acid to the total amountof isophthalic acid of 85:15, the melting point is lowered and hence theheat resistance at the forming time may be deteriorated.

Also, in applications in which retorting is especially performed, in amonomer component mainly constituting thermoplastic polyester resin,dicarboxylic acid is terephthalic acid, and the diol component isethylene glycol and 1,4-butanediol, and the ratio thereof (in the diolcomponent, the ratio of the amount of ethylene glycol to the amount of1,4-butanediol) specified so as to be 20:80 to 80:20 in molar ratio ismost suitable. Further, the range of 60:40 to 30:70 is most suitable. Inthe above-described polyester resin containing polyolefin resin, sincemodified polyolefin resin in resin hinders crystallization of polyesterresin, there arises a problem in that the strength of polyester resin isinsufficient especially in retorting and thus cohesive failure is liableto occur. To solve this problem, polybutylene terephthalate, which hasespecially high crystallization rate, is mixed with polyethyleneterephthalate in a predetermined ratio. Thereby, the crystallization ofpolyester resin is accelerated, and cohesive failure is less liable tooccur even in retorting. Such an effect is especially remarkable inpreventing a phenomenon that in lid material to which a film islaminated, the film is subjected to cohesive failure by water vaporintruding into the film at the retorting time and the film is whitened.By using polyester resin of the above-described composition, such aproblem can be solved. If the amount of polyethylene terephthalate ishigh as compared with the ratio of polyethylene terephthalate topolybutylene terephthalate of 80:20 in molar ratio, the crystallizationrate is not accelerated sufficiently, so that the above-described effectcannot be anticipated. On the other hand, if the amount of polybutyleneterephthalate is high as compared with the ratio of 20:80, the meltingpoint lowers, and hence the heat resistance is deteriorated.

The modified polyolefin resin having a functional group derived fromcarboxylic acid mixed in polyester resin must exist mainly in a granularstate in which the grain diameter is 0.1 to 5 μm in terms of equivalentsphere to improve the impact resistance and also prevent adverseinfluence on the properties such as formability and heat resistance. Inthis case, the phrase “exist mainly” means that at least 30% or more byweight of the whole modified polyolefin resin exists in a state in whichthe grain diameter is 0.1 to 5 μm in terms of equivalent sphere. Also,the weight ratio of the modified polyolefin resin to the entire resinmust be in the range of 3 to 30% by weight.

If modified polyolefin resin is dispersed in polyester resin, widedispersion occurs from very fine grains with a diameter not larger than0.1 μm to large grains with a diameter exceeding 5 μm. The grains with adiameter smaller than 0.1 μm exert no influence on the physicalproperties of mixed resin. On the other hand, the grains with a diameterexceeding 5 μm also do not improve the physical properties such asformability of mixed resin but rather decreases them. Therefore, atleast 30% or more by weight of the whole modified polyolefin resin musthave a diameter in the range of 0.1 to 5 μm in terms of equivalentsphere. From the viewpoint of restraining the decrease in physicalproperties, the ratio of grains with a diameter exceeding 5 μm shouldpreferably be 1% or less by weight. Also, if the ratio of mixed modifiedpolyolefin resin to the entire resin is lower than 3% by weight, theimprovement in impact resistance is insufficient. If the ratio exceeds30% by weight, performance such as formability and heat resistance isdecreased.

The glass-transition temperature of modified polyolefin resin ispreferably 0° C. or lower by the same measuring method as that forpolyester resin. The temperature is further preferably −30° C. If theglass-transition temperature exceeds 0° C., the impact resistance isslightly low, and is low especially at low temperatures. Also, it ispreferable that the Young's modulus be 250 MPa or lower and the breakingelongation be 200% or more at room temperature, and further preferablethat the Young's modulus be 100 MPa or lower and the breaking elongationbe 500% or more. The molecular weight is not subject to any specialrestriction, but it is preferably not lower than 2×10³ and not higherthan 1×10⁶ in number-average molecular weight. If the molecular weightis lower than 2×10³ or exceeds 1×10⁶, the mechanical properties may bedeteriorated and the impact resistance may be decreased, andadditionally, forming may become difficult to do.

The functional group derived from carboxylic acid is contained in anamount of 2 to 20%, preferably 3 to 12%, by weight in carboxylic acidconversion. In this composition range, the affinity with polyester resinand the dispersibility are enhanced to the maximum. As the affinity ofmodified polyolefin resin with polyester resin increases, the effect ofrelaxing interlayer, fracture between different resins is enhanced atthe time of shock. As a result, the impact resistance is increased, andas the result that the cohesion of modified polyester grains isrestrained at the forming time, variations in performance due to formingconditions are decreased. Such an effect can be obtained when the ratioof functional group is 2% or higher by weight in carboxylic acidconversion. On the other hand, if the ratio exceeds 20% by weight, theaffinity with polyester resin decreases inversely, and resultantly theimpact resistance is deteriorated.

In the present invention, it is specified that the amount of modifiedpolyolefin resin existing in mixed resin in a granular state in whichthe grain diameter is 0.1 to 5 μm is in the range of 3 to 25 vol % involume fraction. As described above, the grains with a diameter smallerthan 0.1 μm exert no influence on the physical properties of mixedresin. On the other hand, the grains with a diameter exceeding 5 μm alsodo not improve the physical properties such as formability of mixedresin but rather decreases them. Therefore, only granular modifiedpolyester resin with a diameter of 0.1 to 5 μm in terms of equivalentsphere contributes to the improvement in impact resistance. Since thephysical properties of film having grains of this size can be rearrangedby the absolute value of volume in the whole film, the amount ofmodified polyolefin resin is specified in the range of 3 to 25 vol %. Ifthe volume ratio of modified polyolefin resin is lower than 3 vol %, theimprovement in impact resistance is insufficient, and if it exceeds 25vol %, the performance such as formability is decreased.

Furthermore, the number of modified polyolefin resin grains existing inthe mixed resin layer in a state in which the grain diameter is 0.1 to 5μm in a cube with one side of 10 μm (volume: 1000 μm³) in mixed resin ispreferably 5 to 10⁵, further preferably 50 to 10⁴. If the number issmaller than 5, the improvement in impact resistance is insufficient,and if the number exceeds 10⁵, the performance such as formability isdecreased.

The thickness of resin film consisting of the above-described mixedresin is preferably in the range of 10 to 50 μm. The upper limit valueis determined from the economical viewpoint, and the lower limit valueis determined from the viewpoints of impact resistance and formability.Specifically, if the thickness is not lower than 10 μm, the impactresistance and formability become higher, but if the thickness exceeds50 μm, the cost of resin film increases, and the effect of improvingimpact resistance and formability is saturated.

The following is a description of a manufacturing method for modifiedpolyolefin resin. As a functional group derived from carboxylic acid,carboxylic acid group, carboxylic acid ester group, metal salt ofcarboxylic acid ion, and the like can be cited. Carboxylic acid modifiedpolyolefin can be obtained by copolymerization, graft polymerization, orblock polymerization of monomer containing these functional groups inpolyolefin resin.

As a monomer containing a functional group derived from carboxylic acid,concretely, acrylic acid, methacrylic acid, vinyl acetate, vinylpropionate, maleic acid, maleic anhydride, itaconic acid, unsaturatedcarboxylic acid with the number of carbons of 3 to 8 such asmonomethylester maleate, and metal salt in which the whole or some ofthese acids is neutralized by metal cation of 1 or 2 valences such assodium, potassium, lithium, zinc, magnesium, and calcium can be cited.The degree of neutralization is preferably 20 to 80%, further preferably30 to 70%. A composition formed from modified polyolefin resin with sucha degree of neutralization has a high melt extrusion property.

Also, as carboxylate, methyl acrylate, methyl methacrylate, ethylacrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate,isobutyl acrylate, isobutyl methacrylate, n-butyl acrylate, n-butylmethacrylate, 2-hydroxyethyl carboxylate, 2-hydroxyethyl methacrylate,monomethylester maleate, glycidyl acrylate, glycidyl methacrylate, vinylacetate, acrylamine, acrylamide, and the like can be cited.

Modified polyolefin resin containing a functional group derived fromcarboxylic acid can be obtained by copolymerization, blockpolymerization, or graft polymerization of monomer containing afunctional group derived from carboxylic acid with olefin monomercontaining no functional group derived from carboxylic acid, such asethylene, propylene, 1-butane, 1-pentene, isobutene, isobutylene,butadiene, styrene, and acrylonitrile. Among these, in particular, themodified polyolefin resin obtained by graft polymerization orcopolymerization of carboxylic acid group in polyolefin resin exhibitshigh performance. As such a modified polyolefin resin, Modiper A(manufactured by NOF Corp.), Nucrel (manufactured by Mitsui-DuPontPolychemical Co., Ltd.), Bondine (manufactured by Sumitomo Chemical Co.,Ltd.), Admer (manufactured by Mitsui Chemicals, Inc.), and Tuftec(manufactured by Asahi Chemical Industry Co., Ltd.), and the like can becited.

Also, the modified polyolefin resin in which some of carboxylic acid isneutralized by metal salt can bemused. For such a resin, though theformability is slightly low, the impact resistance is higher. As acommercially available resin, Himilan (manufactured by Mitsui-DuPontPolychemical Co., Ltd.) and the like can be cited. Further, if zincoxide or calcium hydroxide is added when carboxylic acid modifiedpolyolefin resin is melted and dispersed in polyester resin, carboxylgroup in modified polyolefin resin is neutralized by metal ions thereof,and resultantly, a structure in which the carboxylic acid modifiedpolyolefin resin in which some of carboxylic acid is neutralized bymetal salt is dispersed in polyester resin.

By dispersing modified polyolefin resin in polyester resin, a mixedresin, which is used as a raw material, is obtained. As a method fordispersion, there is available, for example, a method in which tworesins are melted and mixed, and after the mixture is kept at atemperature at which one phase is formed, it is cooled to a temperatureat which it is separated into two phases, by which a modified polyolefinresin phase is dispersed in a polyester resin phase by utilizing phaseseparation; a method in which after two resins are melted in a commonsolvent, the solvent is evaporated; a method in which the modifiedpolyolefin resin in which the primary grain diameter has been made finein advance to 1 μm or finer is melted and dispersed at a temperature atwhich the resin does not cohere; a method in which polyester resin ismanufactured by copolymerizing monomer in a solution containing modifiedpolyolefin resin in which the primary grain diameter has been made finein advance to 1 μm or finer and polyester resin forming monomer, and astate in which modified polyolefin resin is dispersed in polyester isestablished; or a method in which two resins are melted and mixed, andmodified polyolefin resin is made fine by a mechanical shearing force.

As an apparatus for mixing and melting, a mixing apparatus such as atumbler blender, a Henschel mixer, and V-type blender, or amelting/mixing apparatus such as an extruder of one axis or two-axes, akneader, and a Banbury type mixer can be used. When these apparatusesare used, the temperature control such as temperature control of mixingapparatus and temperature change is carried out more strictly than inthe ordinary mixing method, the mixing time is prolonged, for example,about three to ten times as compared with the ordinary mixing time, themechanical shearing speed at the mixing time is increased, for example,about two to five times as compared with the ordinary speed, thesemethods are combined, or, after the resins are mixed mechanically byusing, for example, a tumbler blender, they are melted and mixed by anextruder, by which a mixed resin with high dispersibility, in whichgranular modified polyolefin resin with a grain diameter of 0.1 to 5 μmhas been dispersed in advance in thermoplastic polyester resin can beobtained. By film-forming a mixed resin with high dispersibility, whichis obtained by melting and mixing using an extruder, a resin film inwhich the grain diameter of modified polyolefin resin is more uniformcan be obtained. As the result, the performance such as impactresistance is enhanced. By forming a film by inserting such a mixedresin with high dispersibility and uniform grain diameter in an extruderand melting it, the grain diameter distribution of granular resin isnarrowed remarkably as compared with the case where modified polyolefinresin is dispersed while a film is formed, and resultantly a film thatachieves high grade in various performances can be obtained.

On the other hand, unless the effects of the present invention arehindered, an additive, such as a light stabilizer, impact resistanceimproving agent, compatibilizing agent, lubricant, plasticizer,antistatic agent, reaction catalyst, color preventing agent, freeradical inhibitor, plasticizer, oxidation inhibitor, terminal closingagent, heat stabilizer, mold releasing agent, flame retarder,antibacterial agent, and fungistat, may be added to the mixed resin. Thecontent of these additives is preferably not lower than 0.005 weightpart and not higher than 15 weight part, further preferably not lowerthan 0.01 weight part and not higher than 2 weight part, especiallypreferable not lower than 0.05 weight part and not higher than 0.5weight part, with respect to 100 weight part of mixed resin in thepresent invention. If the content is lower than 0.005 weight part, theeffect is insufficient. On the other hand, if the content exceeds 15weight part, the additive is excessive, so that the mechanicalproperties of mixed resin layer are decreased.

As inorganic particles having the effect of improving lubricity,formability, and impact resistance, silica manufactured by the drymethod or wet method, porous silica, colloidal silica, titanium oxide,zirconium oxide, aluminum oxide, calcium carbonate, talc, calciumsulfate, barium sulfate, spinel, iron oxide, calcium phosphate, and thelike can be cited. Also, as organic particles or polymeric organicparticles, vinyl resin particles such as polystyrene particles,crosslinking polystyrene particles, styrene-acrylic crosslinkingparticles, acrylic crosslinking particles, styrene-methacrylate resincrosslinking particles, and methacrylate resin crosslinking particles,and polymeric organic particles consisting of silicone,benzoguanamin-formaldehyde, polytetrafluoroethylene, polyphenolester,phenolic resin, and the like can be cited. The particle diameter andcontent of these particles are not subject to any special restriction.However, in order to achieve the performance to the utmost, the particlediameter is preferably in the range of 0.01 to 5 μm, further preferablyin the range of 0.1 to 2.5 μm. Also, the particle diameter distributionis preferably sharp, and the standard deviation thereof is preferably0.5 or less. Further, the shape of particle is preferably trulyspherical, and the ratio of larger diameter to shorter diameter ispreferably 1.0 to 1.2.

As a reaction catalyst, for example, an alkali metal compound, alkaliearth metal compound, zinc compound, lead compound, manganese compound,cobalt compound, and aluminum compound can be cited, and as a colorpreventing agent, for example, a phosphorus compound can be cited.

As a free radical inhibitor, one or two kinds selected from a phenolbase free radical inhibitor, phosphorus base free radial inhibitor,sulfide base free radical inhibitor, and nitrogen base free radicalinhibitor can be cited.

As a plasticizer, a plasticizer consisting of polyester obtained byterminal esterifying a material obtained by condensation polymerizationof aliphatic polybasic acid with the number of carbons of 2 to 20 oraromatic polybasic acid with the number of carbons of 8 to 20 withrespect to ester derivative or polybasic acid component with the molarratio of the ester derivative of 0 to 2.0 with aliphatic alcohol withthe number of carbons of 2 to 20 by monobasic acid with the number ofcarbons of 2 to 20 or its ester derivative and/or monohydroxy alcoholwith the number of carbons of 1 to 18 can be cited.

As an antistatic agent, a method of kneading an antistatic agentdisclosed in Unexamined-Japanese Patent Publication No. 5-222357 inresin composition, a method of applying an antistatic agent disclosed inUnexamined Japanese Patent-Publication No. 5-1164 on film surface, andthe like method can be used as necessary in order to preventelectrostatic failure such as winding of film on a roll in the filmforming process or contamination adhering to film surface.

As an antibacterial agent, a conventionally known antibacterial agentdisclosed in Unexamined Japanese Patent Publication Nos. 11-48431 and11-138702 can be used as necessary. A polymerization catalyst ofpolyester resin is added to the mixed resin. As a polymerizationcatalyst, an element of at least one kind selected from germanium,antimony, and titanium is contained in an amount preferably not smallerthan 1 ppm and not larger than 500 ppm, further preferably not smallerthan 3 ppm, still further preferably not smaller than 10 ppm. If theamount of element of at least one kind selected from germanium,antimony, and titanium is smaller than 1 ppm, the effect of improvingflavor property is sometimes insufficient. If the amount exceeds 500ppm, foreign matters are produced in polyester and serve as acrystalline nucleus, so that crystallization is liable to occur. In somecases, therefore, the impact resistance is deteriorated or heatresistance is decreased. Among these elements, germanium is especiallyfavorable in terms of flavor property.

A compound used for adding an element of at least one kind selected fromgermanium, antimony, and titanium to the polyester resin of the presentinvention are as follows: As a germanium compound, for example,germanium oxide such as germanium dioxide and crystallization watercontaining germanium hydroxide, hydroxide, or a germanium alkoxidecompound such as germanium tetramethoxide, germanium tetraethoxide,germanium tetrabutoxide, and germanium ethyleneglycoxide, a germaniumphenoxide compound such as germanium phenolate and germaniumβ-naphtholate, a phosphorus containing germanium compound such asgermanium phosphate and germanium phosphite, and germanium acetate canbe cited.

As an antimony compound, diantimony trioxide, antimony trifluoride,antimony acetate, antimony borate, antimony formate, antimonious acid,and the like can be cited.

As a titanium compound, oxide such as titanium dioxide, hydroxide suchas titanium hydroxide, an alcoxide compound such as tetramethoxytitanate, tetraethoxy titanate, tetrapropoxy titanate, tetraisopropoxytitanate, and tetrabutoxy titanate, a glycoside compound such astetrahydroxyethyl titanate, a phenoxide compound, and a compound such asacetate etc. can be cited.

As a method for adding the above-described element to polyester rein,arbitrary one of conventionally known methods can be used, and themethod is not subject to any special restriction. It is preferable thatthe element be added as a polymerization catalyst usually at anarbitrary stage before the manufacture of polyester is finished. As sucha method, in the case of germanium as an example, a method in whichgermanium compound powder is added as it is, a method in which agermanium compound is melted in a glycol compound, which is a startingmaterial for polyester, and is added as described in Japanese PatentPublication No. 54-22234, and the like method can be cited.

When modified polyolefin resin containing carboxylic acid specified inthe present invention is mixed with polyester resin, usually, if thepolymerization catalyst mixed in polyester resin and the oxidationinhibitor generally used for stabilization of vinyl polymer coexist, theresin is deteriorated, and hence the performance is decreased. Themechanism for deteriorating the resin and decreasing the performance isnot necessarily clear, but it is presumed that the oxidation inhibitoracts on the polymerization catalyst and the effect of polymerizationcatalyst is decreased, and in particular, a compound that deterioratespolyester resin is produced. In the present invention, therefore, theratio of the amount X of polymerization catalyst added to the mixedresin to the amount Y of oxidation inhibitor, i.e., X/Y (weight ratio)must be 0.2 or higher. Further, the amount of oxidation inhibitor ispreferably 500 ppm or smaller. As such an oxidation inhibitor, one ortwo kinds selected from phenol base oxidation inhibitor, phosphorus baseoxidation inhibitor, sulfide base oxidation inhibitor, and nitrogen baseoxidation inhibitor can be cited.

Regarding the mechanical properties of resin film consisting of a mixedresin that withstand severe forming, the breakage elongation ispreferably 20% or more, further preferably 50% or more, and the breakagestrength is preferably 20 N/mm² or higher. Herein, the breakageelongation and breakage strength of resin film is determined by using anordinary tensile testing machine. As a tensile testing method, a resincoated layer measuring 5 mm×60 mm is set at a distance between chucks of30 mm, and a tensile test is conducted at a tensile speed of 20 mm/minat a constant temperature of 25° C. When tensile properties at lowtemperature is determined, the same tensile test can be conducted at aconstant temperature of 0 to −5° C. A resin sample for testing may betaken from either of film, resin laminated metal sheet, and formed body.

In the present invention, it is specified that 5 to 40 wt % of pigmentis contained in resin film. In the polyester resin in which modifiedpolyolefin resin is dispersed, the dispersibility of pigment isimproved, and the objective color tone can be obtained by the additionof a small amount of pigment. If the content of pigment is lower than 5wt %, a desired color tone cannot be obtained, and if it exceeds 40 wt%, the formability is decreased. The kind of pigment is not subject toany special restriction. However, unless the effects of the presentinvention are hindered, calcium carbonate, barium sulfate, bariumcarbonate, aerosil, titanium dioxide, zinc white, gloss white, aluminawhite, magnesium carbonate, carbon black, magnetite, cobalt blue, ironoxide red, or the like is used appropriately, by which a metal laminatedsheet or a metal can can be finished so as to have a favorable colortone.

The resin film consisting of the above-described mixed resin has highadhesion to a substrate metal, excellent formability and impactresistance, and flavor property enough for ordinary use as compared withthe ordinary polyester resin, so that it is suitable for use as resinfilm for resin laminated metal sheet.

However, the resin film consisting of the above-described mixed resinmay have insufficient adhesion to a substrate metal when being subjectedto severe forming. Also, many persons are very sensitive to a change inflavor depending on the recent applications, and impose very rigidrequirements. Contrary to such requirements, the resin film consistingof the above-described mixed resin may have an insufficient flavorproperty because it contains an olefin compound.

The above-described problem is solved by using a film in which amodified polyolefin resin layer containing carboxylic acid is laminatedon the resin film consisting of the above-described mixed resin or afilm in which a polyester resin layer containing no olefin resin islaminated. The above-described resin film of a multilayer constructionwill be explained below.

(1) Design is made so that the resin film is a film having aconstruction such that a resin layer (in this description, also referredto as R2 layer) consisting mainly of modified polyolefin resin having afunctional group derived from carboxylic acid is laminated on a resinlayer (in this description, also referred to as R1 layer or mixed resinlayer) consisting of the above-described mixed resin, and when the filmis laminated to a metal sheet, the R2 layer serves as an adhesion layerto a substrate metal.

By the film having the above-described construction, the adhesion afterforming or after heating can be improved dramatically. Further, sincethe modified polyolefin resin layer (R2 layer) has high adhesion to themixed resin layer (R1 layer), separation between layers does not occur,and high adhesion can be kept as a whole. This mechanism is presumed asfollows: Polyester resin is originally a resin having few functionalgroups such as to have chemical bonding to the substrate metal, so thatit does not have so high metal adhesion. On the other hand, modifiedpolyolefin resin having a group derived from carboxylic acid ischaracterized in that the carboxylic acid deriving group contained inthe resin has a strong interaction with the substrate metal, so that ithas very high adhesion. However, it has inferior heat resistance andflavor property, so that it cannot be used as a film for the internalsurface of can. Thereupon, it is expected that if the modifiedpolyolefin resin layer is used as an adhesion layer to the substratemetal and a polyester resin layer is laminated thereon, a film in whichboth of the adhesion and other performance such as heat resistance andflavor property are achieved can be obtained. However, since the meltingviscosity and melting point differ greatly between these resins, theadhesion between layers at the time of laminating these resins is verypoor, and such a double-layer film cannot be manufactured actually. Thepresent invention can achieve two effects at the same time.Specifically, modified polyolefin resin of the same composition as thatof the modified polyolefin resin layer (R2 layer), which is an adhesionlayer, is mixed in the mixed resin layer (R1 layer), by which theadhesion between layers is enhanced to a level at which there is noproblem in terms of manufacture and practical use, and also the modifiedpolyolefin resin mixed in the polyester resin is formed into a granularshape, by which the formability and impact resistance can be improved.

The film in which the mixed resin layer (R1 layer) and the modifiedpolyolefin resin layer (R2 layer) are laminated can be obtained by theordinary double-layer resin extruding method. Specifically, by using twoextruding machines, mixed resin in which granular modified polyolefinresin with a grain diameter of 0.1 to 5 μm is dispersed in advance inthermoplastic polyester resin and resin consisting mainly of modifiedpolyolefin resin having a functional group derived from carboxylic acidare inserted in separate extruding machines, respectively, as rawmaterial resins of R1 and R2 layers, and the resins are melted to atemperature above the respective melting point and are extruded from oneT die in a state of being laminated by the feed block method or themulti-manifold method to form a film as a double-layer film by beingcooled with a cooling roll etc. and then the film is laminated to ametal sheet. Alternatively, the molten resin is extruded directly on themetal sheet, and then is laminated by being held between the coolingrolls. Thereby, a resin layer of double layers can be manufactured. Asthe T die method, it is especially preferable that the resin layer bemanufactured by the multi-manifold method in which the meltingtemperatures of a plurality of resins can be controlled precisely.

Also, as another manufacturing method, since the surface tension ofmodified polyolefin resin is lower than that of polyester resin, byutilizing a property such that modified polyolefin resin is concentratedon the surface of mixed resin during the time when molten mixed resin iscooled, both resins are inserted into one extruding machine, and thecooling rate is decreased when the resins are melted and mixed andextruded from a T die, by which the modified polyolefin resin isconcentrated on the surface of mixed resin. By this method as well, alaminated film of both resins can be manufactured.

The thickness ratio R1/R2 of R1 layer to R2 layer is preferablyR1/R2=1/1 to 20/1, further preferably R1/R2=5/1 to 10/1, in acomposition such that the mechanical properties such as formability andimpact resistance and adhesion are at the maximum. If the R1 layer isthinner than this, the mechanical properties are deteriorated greatly.On the other hand, if the R2 layer is thinner than this, the adhesion isdeteriorated. Further, the optimum thickness of modified polyolefinresin of R2 layer is preferably 1 to 10 μm, further preferably 1 to 5μm. If the thickness is smaller than 1 μm, the adhesion is insufficient.On the other hand, if the thickness exceeds 10 μm, high impactresistance and formability of olefin dispersing polyester resin of R1layer are lost. Similarly, the optimum thickness of modified polyolefindispersing polyester resin of R1 layer is preferably 10 to 50 μm,further preferably 15 to 25 μm. If the thickness is smaller than 10 μm,the impact resistance and formability are insufficient. On the otherhand, if the thickness exceeds 50 μm, these properties are not enhanced,being disadvantageous in terms of cost.

Furthermore, the optimum composition of modified polyolefin resin of R2layer is, as in the case of modified polyolefin in mixed resin of R1layer, a composition that contains preferably 2 to 20 wt %, furtherpreferably 3 to 12 wt %, of a functional group derived from carboxylicacid, by weight percentage in carboxylic acid conversion. The reason forthis is that regarding adhesion after severe forming or shock, not onlythe adhesion of resin to a substrate metal but also the adhesion ofmixed resin of R1 layer to modified polyolefin resin of R2 layer isimportant, and the adhesion of these two layers depends basically on theinteraction between modified polyolefin resins, so that resincomposition closer to each other is advantageous. Herein, weightpercentage in carboxylic acid conversion means that all functionalgroups derived from carboxylic acid contained in modified polyolefinresin are converted into carboxylic acid by hydrolysis or neutralizationusing acid, and the amount of carboxylic acid group (—COOH) in theoriginal modified polyolefin resin is expressed by weight percentage.

(2) Design is made so that the resin film is a film having aconstruction such that a polyester resin layer (in this description,also referred to as R0 layer) containing polyethylene terephthalateand/or isophthalic acid copolymerized polyethylene terephthalate as amain basic skeleton is laminated on the mixed resin layer (R1 layer),and when the film is laminated to a metal sheet, the R0 layer serves asan outermost layer.

The polyester resin containing polyethylene terephthalate and/orisophthalic acid copolymerized polyethylene terephthalate as a mainbasic skeleton means polyester resin in which the sum of a portion inwhich only ethylene glycol and tereophthalic acid in the polyester resinskeleton are a unit and/or a portion in which ethylene glycol andtereophthalic acid and isophthalic acid are a unit accounts for 90% ormore by weight. In other portions, as the acid component, various kindsof aromatic dicarboxylic acids and aliphatic dicarboxylic acids may becopolymerized arbitrarily.

Since the R1 layer is soft, in copolymerized polyester resin, the heatresistance and flavor property are sometimes inferior. A two-layerconstruction is provided in which the resin layer (R1 layer) consistingof mixed resin in which modified polyolefin resin is dispersed is made alower layer, and the polyester resin (R0 layer) containing no olefin ismade an upper layer, and the R0 layer is made a layer that comes intocontact with the content, by which the flavor property of film isdramatically enhanced. Thereby, the flavor property can be enhanced to alevel that meets the above-described rigid requirements. A slight olefinportion contained in polyester resin provides greater sorption ofterpene hydrocarbon such as d-limonene, which is a flavor component,than the polyester portion, so that the sorption of flavor is great as awhole as compared with polyester resin containing no olefin. Therefore,when the flavor-containing content comes into contact with the film, alarger amount of flavor component transfers from the content to thefilm. To restrain such a phenomenon, it is effective to provide apolyester resin layer containing no olefin component on a polyesterresin layer containing olefin component. Also, the mechanical propertiessuch as formability and impact resistance can be improved.

The optimum thickness of the upper layer (R0 layer) is preferably 1 to10 μm, further preferably 3 to 5 μm. If the thickness is smaller than 1μm, the effect of restraining sorption of flavor component can scarcelybe expected. On the other hand, if the thickness exceeds 10 μm, highimpact resistance and formability of olefin dispersed polyester resin ofthe lower layer is lost. The optimum thickness of the lower layer (R1layer) is preferably 10 to 50 μm, further preferably 15 to 25 μm. If thethickness is smaller than 10 μm, the impact resistance and formabilityare insufficient. On the other hand, even if the thickness exceeds 50μm, these properties are not enhanced, being disadvantageous in terms ofcost.

The total film thickness of R1 layer and R0 layer is preferably in therange of 10 to 50 μm. The upper limit value is determined from theeconomical viewpoint, and the lower limit value is determined from theviewpoints of impact resistance and formability. Specifically, if thetotal thickness is not smaller than 10 μm, the impact resistance andformability becomes higher, but if the total thickness exceeds 50 μm,the cost of resin film increases, and the effect of improving impactresistance and formability is saturated.

The thickness ratio R1/R0 of the lower layer (R1 layer) to the upperlayer (R0 layer) is preferably R1/R2=2/1 to 10/1, further preferably 5/1to 10/1, in a composition such that the mechanical properties such asformability and impact resistance and flavor-property are at themaximum. If the R0 layer is thicker than this, the mechanical propertiesare deteriorated greatly. On the other hand, if the R0 layer is thinnerthan this, the R0 and R1 layers do not have uniform film thickness inthe line direction and the width direction, so that the performancevaries and becomes poor.

For the polyester resin of R0 layer, the content of diethylene glycol ispreferably 1.5% or lower by weight, further preferably 0.9% or lower byweight. If the content of diethylene glycol is high, deterioration ofpolymer progresses due to heating treatment such as drying and printingat the forming time, and hence cracks or pinholes are produced, so thatthe impact resistance and flavor property are sometimes deteriorated.

The intrinsic viscosity of polyester resin of R0 layer is preferably 0.3to 2.0 dl/g, further preferably 0.3 to 1.5 dl/g, still furtherpreferably 0.5 to 1.0 dl/g. If the intrinsic viscosity is lower than 0.3dl/g, the mixing with modified polyolefin resin is remarkably difficult.As the result of nonuniform dispersion of modified polyolefin resin, themechanical strength and impact resistance of polyester resin may bedecreased. On the other hand, if the intrinsic viscosity exceeds 2.0dl/g, the formability is poor because of low viscosity, so that it maybecome difficult to manufacture a uniform film. The intrinsic viscosityis measured by the method specified in JIS K7367-5. It is measured ino-chlorophenol at 25° C. in a concentration of 0.005 g/ml, and isdetermined by the formula of intrinsic viscosity=(T−T₀)/(T₀×c). In thisformula, c expresses resin concentration per 100 ml of solution in gram,and T₀ and T express drop time in a capillary viscometer of solvent andresin solution, respectively.

The glass-transition temperature (Tg) of the polyester resin of R0 layeris preferably 30 to 100° C., further preferably 50 to 80° C. If theglass-transition temperature is lower than 30° C., a flaw etc. areliable to be produced by a temperature rise at the forming time becauseof deteriorated heat resistance of polyester resin. On the other hand,if the glass-transition temperature exceeds 100° C., inversely theformability is sometimes deteriorated. Also, the low-temperaturecrystallization temperature (Tc) is usually 70 to 210° C., preferably 80to 200° C. The melting point (Tm) is usually 210 to 265° C., preferably220 to 260° C. If the low-temperature crystallization temperature islower than 70° C., crystallization is liable to occur, so thatcrystallization occurs at the time of retorting, by which the film iseasily cracked or separated. On the other hand, if the low-temperaturecrystallization temperature exceeds 210° C., the mechanical strength isdeteriorated. If the melting point is lower than 210° C., resin isdeteriorated by heat at the forming time, so that cracks or pinholes areliable to be produced. On the other hand, if the melting point exceeds265° C., crystallization progresses due to heating treatment such asdrying and printing at the forming time, and hence cracks or pinholesare also liable to be produced. The above-described glass-transitiontemperature, low-temperature crystallization temperature, and crystalmelting point are obtained by measuring endothermic peak temperature atthe time of temperature rise using a differential scanning calorimeter(DSC). The measurement is made under conditions of sample amount of 10mg and temperature rise rate of 10° C./min.

The film in which the mixed resin layer (R1 layer) and the polyesterresin layer (R0 layer) containing polyethylene terephthalate and/orisophthalic acid copolymerized polyethylene terephthalate as a mainbasic skeleton are laminated can be obtained by the ordinarydouble-layer resin extruding method. Specifically, by using twoextruding machines, mixed resin in which granular modified polyolefinresin with a grain diameter of 0.1 to 5 μm is dispersed in advance inthe thermoplastic polyester resin as described in any one of claims 1 to8 and polyester resin containing polyethylene terephthalate and/orisophthalic acid copolymerized polyethylene terephthalate as amain-basic skeleton are inserted in separate extruding machines,respectively, as raw material resins of R1 and R0 layers, and the resinsare melted to a temperature above the respective melting point and areextruded from one T die in a state of being laminated by the feed blockmethod or the multi-manifold method to form a film as a double-layerfilm by being cooled with a cooling roll etc. and then the film islaminated to a metal sheet. Alternatively, the molten resin is extrudeddirectly on the metal sheet, and then is laminated by being held betweenthe cooling rolls. Thereby, a resin layer of double layers can bemanufactured. As the T die method, it is especially preferable that theresin layer be manufactured by the multi-manifold method in which themelting temperatures of a plurality of resins can be controlledprecisely.

Also, unless the effects of the present invention are hindered, anadditive, such as a light stabilizer, impact resistance improving agent,compatibilizing agent, lubricant, plasticizer, antistatic agent,reaction catalyst, color preventing agent, free radical inhibitor,plasticizer, antistatic agent, terminal closing agent, oxidationinhibitor, heat stabilizer, mold releasing agent, flame retarder,antibacterial agent, and fungistat, may be added to the polyester resinof R0 layer. The content of these additives is preferably not lower than0.005 weight part and not higher than 15 weight part, further preferablynot lower than 0.01 weight part and not higher than 2 weight part,especially preferable not lower than 0.05 weight part and not higherthan 0.5 weight part, with respect to 100 weight part of polyester resinof R0 layer. If the content is lower than 0.005 weight part, the effectis insufficient. On the other hand, the content exceeds 15 weight part,the additive is excessive, so that the component contained in thepolyester resin phase decreases the mechanical properties.

As inorganic particles having the effect of improving lubricity,formability, and impact resistance, silica manufactured by the drymethod or wet method, porous silica, colloidal silica, titanium oxide,zirconium oxide, aluminum oxide, calcium carbonate, talc, calciumsulfate, barium sulfate, spinel, iron oxide, calcium phosphate, and thelike are cited. Also, as organic particles or polymeric organicparticles, vinyl resin particles such as polystyrene: particles,crosslinking, polystyrene particles, styrene-acrylic crosslinkingparticles, acrylic crosslinking particles, styrene-methacrylate resincrosslinking particles, and methacrylate resin crosslinking particles,and particles consisting of silicone, benzoguanamin-formaldehyde,polytetrafluoroethylene, polyphenolester, phenolic resin, and the likecan be cited. The particle diameter and content of these particles arenot subject to any special restriction. However, in order to achieve theperformance to the utmost, the particle diameter is preferably in therange of 0.01 to 5 μm, further preferably in the range of 0.1 to 2.5 μm.Also, the particle diameter distribution is preferably sharp, and thestandard deviation thereof is preferably 0.5 or less. Further, the shapeof particle is preferably truly spherical, and the ratio of largerdiameter to shorter diameter is preferably 1.0 to 1.2.

As a reaction catalyst, for example, an alkali metal compound, alkaliearth metal compound, zinc compound, lead compound, manganese compound,cobalt compound, and aluminum compound can be cited, and as a colorpreventing agent, for example, a phosphorus compound can be cited.

As a free radical inhibitor, one or two kinds selected from a phenolbase free radical inhibitor, phosphorus base free radical inhibitor,sulfide base free radical inhibitor, and nitrogen base free radicalinhibitor can be cited.

As a plasticizer, a plasticizer consisting of polyester obtained byterminal esterifying a material obtained by condensation polymerizationof aliphatic polybasic acid with the number of carbons of 2 to 20 oraromatic polybasic acid with the number of carbons of 8 to 20 withrespect to ester derivative or polybasic acid component with the molarratio of the ester derivative of 0 to 2.0 with aliphatic alcohol withthe number of carbons of 2 to 20 by monobasic acid with the number ofcarbons of 2 to 20 or its ester derivative and/or monohydroxy alcoholwith the number of carbons of 1 to 18 can be cited.

As an antistatic agent, a method of kneading an antistatic agentdisclosed in Unexamined Japanese Patent Publication No. 5-222357 inresin composition, a method of applying an antistatic agent disclosed inUnexamined Japanese Patent Publication No. 5-1164 on film surface, andthe like method can be used as necessary in order to preventelectrostatic failure such as winding of film on a roll in the filmforming process or contamination adhering to film surface.

As an antibacterial agent, a conventionally known antibacterial agentdisclosed in Unexamined Japanese Patent Publication Nos. 11-48431 and11-138702 can be used as necessary.

The polyester resin of R0 layer preferably contains 1 to 500 ppm;further preferably 3 to 300 ppm, of an element of at least one kindselected from germanium, antimony, and titanium as a polymerizationcatalyst. If the amount of element of at least one kind selected fromgermanium, antimony, and titanium is smaller than 1 ppm, the effect ofimproving flavor property is sometimes insufficient. If the amountexceeds 500 ppm, foreign matters are produced in polyester and serve asa crystalline nucleus, so that crystallization is liable to occur. Insome cases, therefore, the impact resistance is deteriorated or heatresistance is decreased. Among these elements, germanium is especiallyfavorable in terms of flavor property.

A compound used for adding an element of at least one kind selected fromgermanium, antimony, and titanium to the resin of the present inventionare as follows: As a germanium compound, for example, germanium oxidesuch as germanium dioxide and crystallization water containing germaniumhydroxide, hydroxide, or a germanium alkoxide compound such as germaniumtetramethoxide, germanium tetraethoxide, germanium tetrabutoxide, andgermanium ethyleneglycoxide, a germanium phenoxide compound such asgermanium phenolate and germanium β-naphtholate, a phosphorus containinggermanium compound such as germanium phosphate and germanium phosphite,and germanium acetate can be cited.

As an antimony compound, diantimony trioxide, antimony trifluoride,antimony acetate, antimony borate, antimony formate, antimonious acid,and the like can be cited.

As a titanium compound, oxide such as titanium dioxide, hydroxide suchas titanium hydroxide, an alcoxide compound such as tetramethoxytitanate, tetraethoxy titanate, tetrapropoxy titanate, tetraisopropoxytitanate, and tetrabutoxy titanate, a glycoside compound such astetrahydroxyethyl titanate, a phenoxide compound, and a compound such asacetate etc. can be cited.

As a method for adding the above-described element to polyester,arbitrary one of conventionally known methods can be used, and themethod is not subject to any special restriction. It is preferable thatthe element be added as a polymerization catalyst usually at anarbitrary stage before the manufacture of polyester is finished. As sucha method, in the case of germanium as an example, a method in whichgermanium compound powder is added as it is, a method in which agermanium compound is melted in a glycol compound, which is a startingmaterial for polyester, and is added as described in Japanese PatentPublication No. 54-22234, and the like method can be cited.

For the polyester resin of R0 layer of the present invention, thecontent of acetaldehyde in the resin is preferably not higher than 10ppm, further preferably not higher than 7 ppm from the viewpoint offlavor property. If the content of acetaldehyde exceeds this range,especially 10 ppm, the flavor property is sometimes deteriorated. Themethod for limiting the content of acetaldehyde to 10 ppm or lower isnot subject to any special restriction. For example, a method can becited in which polyester resin is formed into a film, the polyesterresin being obtained by a method in which resin is heat-treated at atemperature below the melting point of polyester under a reducedpressure or in an inert gas atmosphere to remove acetaldehyde producedby thermal decomposition at the time when polyester resin ismanufactured by condensation polymerization etc. Preferably, a methodshould be used in which polyester resin that is obtained by solid-phasepolymerizing resin at a temperature higher than 150° C. and lower thanthe melting point under a reduced pressure or in an inert gasatmosphere.

Also, the polyester resin in accordance with the present inventionpreferably has less oligomer consisting of a cyclic trimer etc. in resinfrom the viewpoint of flavor property. In particular, the content ofcyclic trimer is preferably 0.9% or lower by weight, further preferably0.7% or lower by weight. If the content of oligomer in resin exceedsthis range, especially 0.9% by weight, the flavor property is sometimesdeteriorated. The method for limiting the content of oligomer to 0.9% orlower by weight is not subject to any special restriction, and thiscontent of oligomer can be achieved by using the same method as theabove-described method for reducing the content of acetaldehyde.

When an oxidation inhibitor is added to the R0 layer, the added amountshould preferably be the same as the added amount to the R1 layer tominimize the influence on the R1 layer.

(3) Design is made so that the resin film is a film having a three-layerconstruction of R0 layer/R1 layer/R2 layer such that the polyester resinlayer (R0 layer) containing polyethylene terephthalate and/orisophthalic acid copolymerized polyethylene terephthalate as a mainbasic skeleton is laminated on one surface of the resin layer (R1 layer)consisting of mixed resin, and the resin layer (R2 layer) consistingmainly of modified polyolefin resin having a functional group derivedfrom carboxylic acid is laminated on the other surface of the R1 layer;and when the film is laminated to a metal sheet, the R0 layer serves asan outermost layer.

This film is formed by laminating the R0 layer described in the aboveitem (1) on the R1 layer of the resin film of a two-layer constructionconsisting of R1 layer and R2 layer described in the above item (2).This film having a three-layer construction has high adhesion to thesubstrate metal and high flavor property. The construction andoperation/effect of the R1 layer, R0 layer, and R2 layer are the same asthose described in the above items (1) and (2). Further, such athree-layer construction enhances adhesion and a stress relaxing effect,so that defects are less liable to be produced in forming, and thus theformability is enhanced dramatically.

The above-described film having a three-layer construction of R0layer/R1 layer/R2 layer can be obtained by the ordinary extruding methodfor a double-layer resin. Specifically, by using three extrudingmachine, mixed resin in which granular modified polyolefin resin with agrain diameter of 0.1 to 5 μm is dispersed in advance in thethermoplastic polyester resin as described in any one of claims 1 to 8is inserted in the extruding machine as a raw material of R1 layer andis melted, and at the same time, polyester resin containing polyethyleneterephthalate and/or isophthalic acid copolymerized polyethyleneterephthalate as a main basic skeleton and modified polyolefin resinhaving a functional group derived from carboxylic acid are inserted inextruding machines separate from the above-described extruding machine,respectively, as raw material resins of R0 and R2 layers, and the resinsare melted to a temperature above the respective melting point and areextruded from one T die in a state of being laminated by the feed blockmethod or the multi-manifold method to form a film as a multi-layer filmby being cooled with a cooling roll etc. and then the film is laminatedto a metal sheet. Alternatively, the molten resin is extruded directlyon the metal sheet, and then is laminated by being held between thecooling rolls. Thereby, a resin layer of multiple layers can bemanufactured. As the T die method, it is especially preferable that theresin layer be manufactured by the multi-manifold method in which themelting temperatures of a plurality of resins can be controlledprecisely.

Furthermore, in any case, the resin film can be formed so as to have alayer construction such that another polyester resin layer is laminatedon the mixed resin layer (R1 layer) or the polyester resin layer (R0layer) containing polyethylene terephthalate and/or isophthalic acidcopolymerized polyethylene terephthalate as a main basic skeleton. Inthis case, the polyester resin that is a raw material of the third layeris inserted in a separate extruding machine and is melted, and is pouredinto a T die simultaneously with other resins and is extruded throughone port, by which a resin film is manufactured. When the resin layer(R2 layer) consisting mainly of modified polyolefin resin having afunctional group derived from carboxylic acid exists, design must bemade so that the R2 layer is on the substrate metal side.

In the resin films described in the above items (1) to (3), it isspecified that five to 40 wt % of pigment is contained in resin film. Inthe polyester resin in which modified polyolefin resin is dispersed, thedispersibility of pigment is improved, and the objective color tone canbe obtained by the addition of a small amount of pigment, so that it ispreferable to add pigment to the R1 layer. If the content of pigment inthe resin film is lower than 5 wt %, a desired color tone cannot beobtained, and if it exceeds 40 wt %, the formability is decreased. Thekind of pigment is not subject to any special restriction. However,unless the effects of the present invention are hindered, calciumcarbonate, barium sulfate, barium carbonate, aerosil, titanium dioxide,zinc white, gloss white, alumina white, magnesium carbonate, carbonblack, magnetite, cobalt blue, iron oxide red, or the like is usedappropriately, by which a metal laminated sheet or a metal can can befinished so as to have a favorable color tone.

In the present invention, the metal sheet is not subject to any specialrestriction. However, a metal sheet formed of iron and aluminum ispreferable in terms of formability. In the case of metal sheet formed ofiron, in order to improve the resin adhesion and corrosion resistance,an inorganic oxide film layer, for example, a chemical conversioncoating layer represented by chromic acid treatment, phosphatetreatment, chromic acid/phosphate treatment, electrolytic chromic acidtreatment, chromate treatment, chrome chromate treatment, and the likemay be provided on the surface of metal sheet. Also, a malleable metalplating layer, for example, a plating layer of nickel, tin, zinc,aluminum, gun metal, brass, or the like may be provided. Also, theplating layer having the amount of plating of 0.5 to 15 g/m² in the caseof tin plating and 1.8 to 20 g/m² in the case of nickel or aluminumplating is especially preferable in terms of formability and resinadhesion. The thickness of such a metal sheet is usually 0.01 to 5 mm,preferably 0.1 to 2 mm. On one surface or both surfaces of the metalsheet, a resin laminated layer coated with the above-described resincomposition layer in accordance with the present invention is formed.

In the case of metal sheet in which iron is used as a raw material, thesteel sheet subjected to electrolytic chromate treatment defined in theeighth invention is especially preferable in terms of adhesion to theresin film of the present invention, corrosion resistance, andmanufacturing cost. Since the resin in accordance with the presentinvention has high adhesion after forming or heating, the optimum rangeof metallic chromium and chromium oxide is wider than that of theconventional resin. However, it has been found that when higherperformance is demanded, the range of the present invention is theoptimum one. The reason why the lower limit of the amount of metallicchromium in metallic chromium layer is specified so as to be 50 mg/m² isthat if the amount is smaller than 50 mg/m², the corrosion resistanceand adhesion after forming are sometimes insufficient. The reason whythe upper limit thereof is specified so as to be 200 mg/m² is that ifthe amount exceeds 200 mg/m², the effect of improving the corrosionresistance and adhesion after forming is saturated, and inversely themanufacturing cost is increased. The reason why the lower limit ofmetallic chromium conversion amount of the amount of chromium inchromium oxide is specified so as to be 3 mg/m² is that if the amount issmaller than 3 mg/m², the adhesion is sometimes deteriorated. The reasonwhy the upper limit thereof is specified so as to be 30 mg/m² is that ifthe amount exceeds 30 mg/m², the color tone is deteriorated, and alsothe adhesion becomes inferior.

The reason why the plane orientation coefficient in the directionparallel with the film surface of resin film is specified so as to be0.010 or lower is that the resin film in this range especially has highformability. As the plane orientation coefficient increases, theformability becomes inferior. This is because oriented crystals hinderplastic deformation as described above. The range of plane orientationcoefficient in accordance with the present invention is at a level atwhich adverse influence is not substantially exerted on the formability.Also, even in the range of plane orientation coefficient of the aboveitem (24), sufficiently high impact resistance is provided as comparedwith the prior art. However, considering the required formability andimpact resistance, the plane orientation coefficient can also beincreased intentionally to 0.010 or higher to obtain still higher impactresistance. The above-described film orientation can be obtained bylaminating a stretched film to the metal sheet. Specifically, a film isstretched in the one-axis or two-axis direction by the publicly knownmethod at the time of film manufacture to provide stretch orientation,and the stretched film is thermally laminated by being controlled sothat the orientation remains at the laminating time, by which the filmorientation can be obtained. Regarding the stretching of film, two-axisstretching is especially superior from the viewpoint of mechanicalproperties.

As the method for manufacturing a resin laminated metal sheet, thepublicly known method can be used. An especially preferable method isone in which a resin film is pushed, by using a rotating roll, on ametal sheet heated to a temperature in the range of the melting point ofpolyester resin in mixed resin of R1 layer minus 70° C. to the meltingpoint thereof plus 30° C. to laminate the resin film to the metal sheet.If the heating temperature is lower than the melting point of polyesterresin minus 70° C., the adhesion to metal sheet is insufficient, and ifit exceeds the melting point of polyester resin plus 30° C., the filmlayer fuses to the laminate roll. Since the resin of the presentinvention has high formability and adhesion after heating, the optimumrange of manufacturing conditions in film laminating becomes wider thanthat in the case of the conventional resin, so that labor saving andstabilization in terms of manufacture control and quality control can beprovided advantageously.

As the laminating film, both a stretch oriented-film and a non-stretchedfilm can be used. In particular, when the stretched film is used,control is needed so that the degree of orientation is made a targetvalue by temperature control at the thermal laminating time as describedabove.

When a resin laminated metal sheet is manufactured, a direct laminatingmethod in which molten resin is extruded directly on a metal sheet, andthen is laminated by being held between cooling rolls as described belowis preferable.

When a resin film consisting of mixed resin is laminated to a metalsheet, a mixed resin in which granular modified polyolefin resin with agrain diameter of 0.1 to 5 μm is dispersed in advance in thethermoplastic polyester resin as described herein is inserted in anextruding machine as a resin used for raw material, the above-describedresin used for raw material is heated to a temperature in the range ofthe melting point of polyester resin in that resin plus 10° C., to themelting point plus 50° C. and is melted, and then the molten resin isdirectly extruded from a T die and is laminated on the surface of metalsheet.

When a resin film consisting of R1 layer and R0 layer is laminated to ametal sheet, a mixed resin in which granular modified polyolefin resinwith a grain diameter of 0.1 to 5 μm is dispersed in advance in thethermoplastic polyester resin as described herein is inserted in anextruding machine as a resin used for raw material of R1 layer, and atthe same time, a resin consisting of polyester resin containingpolyethylene terephthalate and/or isophthalic acid copolymerizedpolyethylene terephthalate as a main basic skeleton is inserted in aseparate extruding machine as a resin used for raw material of R0 layer.After these resins are heated to a temperature in the range of themelting point of polyester resin in the R1 layer plus 10° C. to themelting point plus 50° C. and are melted, they are directly extruded intwo layers from a T die and are laminated on the surface of metal sheetso that the R1 layer is on the metal sheet side in a state in which theR1 layer and the R0 layer are laminated.

When a resin film consisting of R1 layer and R2 layer is laminated to ametal sheet, a mixed resin in which granular modified polyolefin resinwith a grain diameter of 0.1 to 5 μm is dispersed in advance in thethermoplastic polyester resin as described herein is inserted in anextruding machine as a resin used for raw material of R1 layer, and atthe same time, a resin consisting mainly of modified polyolefin resinhaving a functional group derived from carboxylic acid is inserted in aseparate extruding machine as a resin used for raw material of R2 layer.After these resins are heated to a temperature in the range of themelting point of polyester resin in the R1 layer plus 10° C. to themelting point plus 50° C. and are melted, they are directly extruded intwo layers from a T die and are laminated on the surface of metal sheetso that the R2 layer is on the metal sheet side in a state in which theR1 layer and the R2 layer are laminated.

When a resin film of three-layer construction of R0 layer/R1 layer/R2layer is laminated to a metal sheet, a mixed resin in which granularmodified polyolefin resin with a grain diameter of 0.1 to 5 μm isdispersed in advance in the thermoplastic polyester resin as describedherein is inserted in an extruding machine as a resin used for rawmaterial of R1 layer, and at the same time, a resin consisting ofpolyester resin containing polyethylene terephthalate and/or isophthalicacid copolymerized polyethylene terephthalate as a main basic skeletonand a resin consisting mainly of modified polyolefin resin having afunctional group derived from carboxylic acid are inserted in extrudingmachines separate from the above-described extruding machine,respectively, as resins used for raw materials of R0 and R2 layers.After these resins are heated to a temperature in the range of themelting point of polyester resin in the R1 layer plus 10° C. to themelting point plus 50° C. and are melted, they are directly extruded inthree layers from a T die and are laminated on the surface of metalsheet so that the R2 layer is on the metal sheet side, the R1 layer isan intermediate layer, and the R0 layer is an outermost layer in a statein which the R0 layer, the R1 layer, and the R2 layer are laminated.

If the temperature at which resin is melted is lower than the meltingpoint of polyester resin plus 10° C., the viscosity of resin isremarkably inferior, so that the quality stability and productivity aredeteriorated. If the temperature exceeds the melting point of polyesterresin plus 50° C., there arise problems of adhesion to laminate roll,intrusion of air bubbles. and deteriorated resin. The temperature ispreferably not higher than the melting point of polyester resin plus 40°C. Also, the temperature of metal sheet is preferably in the range ofthe melting point of polyester resin in mixed resin of R1 layer minus70° C. to the melting point plus 30° C.

The resin in accordance with the present invention need not becontrolled strictly even under the manufacturing conditions in extrusionlaminating. Therefore, labor saving and stabilization in terms ofmanufacture control and quality control can be provided advantageously.Also, such a mixed resin having uniform grain diameter and highdispersibility is inserted in the extruding machine to form a film.Therefore, the grain diameter distribution of granular resin is narrowedremarkably as compared with the case where modified polyolefin resin isdispersed while a film is formed, and resultantly a film that achieveshigh grade in various performances can be obtained.

The reason why the resin film is limited to one that is coated by theextrusion laminating method is that the extrusion laminating method issuperior to the ordinary film laminating method from the viewpoint ofinclusion of air bubbles at the laminating time. In the general filmlaminating method, in particular, as the laminating speed increases, airbubbles are liable to be included. The included air bubbles not onlydecrease adhesion to a substrate metal sheet but also exert an adverseinfluence on impact resistance. The inventors found out that sincestresses concentrate in the edge portion of air bubble at the time ofshock, this portion is brittle and serves as a starting point of filmfracture. Further, a difference in manufacturing cost between theprocess in which resin is formed into a film and laminated and theprocess in which resin is directly extruded and laminated is also anadvantage of the extrusion laminating method.

The resin in accordance with the present invention can be manufacturedby the extrusion laminating method that cannot be used for theconventional polyester resin because the resin of the present inventioncan provide sufficient performance substantially even in a non-orientedstate. The conventional polyester resin requires strict control oforientation amount, so that it cannot be manufactured by directextrusion that cannot be controlled strictly. As compared with this, theresin of the present invention also has a great advantage in terms ofmanufacture.

For the resin laminated metal sheet in accordance with the presentinvention, a metal sheet has only to be coated with the resin film ofthe present invention. The publicly known resin film may be laminated asnecessary to the lower layer and/or the upper layer of resin film of thepresent invention, and a metal sheet may be coated with the laminatedfilm.

In the present invention, unless the effects of the present inventionare hindered, a primer layer may be provided as an adhesion layer tometal sheet. Although the laminated metal sheet of the present inventionhas high primary adhesion between resin layer and metal sheet and highadhesion after forming, in a severer corrosive environment or in anenvironment in which higher adhesion is required, a primer layer can beprovided to provide characteristics that meet the requirement. Forexample, when the laminated metal sheet is used as a metallic can, ifmore corrosive content is put into the can, the content intrudes aninterface with metal sheet through the resin layer, by which the metalsheet may be corroded, and the adhesion to film may be deteriorated. Insuch a case, a proper primer layer is provided to prevent the resinlayer from being separated. When the R2 layer is absent, it is effectiveto provide the primer layer as an adhesion layer.

The kind of primer is not subject to any special restriction, and thepublicly known primer layer can also be used. For example, a water-basedispersing agent of polyester resin base disclosed in Japanese PatentPublication No. 60-12233, an epoxy-base primer disclosed in JapanesePatent Publication No. 63-13829, and a polymer having various functionalgroups disclosed in Unexamined Japanese Patent Publication No. 61-149341can be cited. Also, a method for forming a primer layer is not subjectto any special restriction. A primer paint may be applied on the metalsheet and dried, or a primer paint may be applied on the film of thepresent invention and dried. Alternatively, a primer film may belaminated to the metal sheet, or a film formed by affixing a primerlayer to the film of the present invention may be laminated.

The resin film in accordance with the present invention can be usedsuitably to coat the internal surface of a two-piece metallic canmanufactured by drawing or ironing. Also, since the film in accordancewith the present invention has good metal adhesion and formability as acoating film for a lid portion of two-piece can or a sidewall, lid, andbottom of three-piece can, it can be favorably used in this application.Also, the resin laminated metal sheet coated with the film has highformability, impact resistance, and adhesion, it is suitable as amaterial used for a thin-wall deep drawn can in which a decrease inmaterial thickness progresses and especially severe forming is forced.

Also, since the resin laminated metal sheet coated with the film canprevent the film from being whitened at the retorting time, it cansuitably be used as a can member used for a can lid or a can bottom thatis required to prevent the film from being whitened, for example, a lidmember of two-piece can or a lid member or a sidewall member ofthree-piece can.

EXAMPLES Example 1

Modified polyolefin resin with group derived from carboxylic acid havinga primary grain diameter of 0.3 μm, which was a starting raw material,was cold blended with polyester resin in a blending ratio given inTables 1 and 2 by using a tumbler blender, and then the blended resinwas melted and kneaded at 260° C. by using a two-axis extruding machine,by which a raw material pellet of polyester resin in which modifiedpolyolefin resin was dispersed was obtained. The obtained raw materialresin pellet was extruded from a T die by using a one-axis extrudingmachine, by which a resin film with a thickness of 5 to 55 μm wasmanufactured.

The used polyester resin and modified polyolefin resin with groupderived from carboxylic acid were as follows:

1. Polyester Resin

(1) PET/I (18) Ethylenephthalate-ethyleneisophthalate copolymerizedresin with a ratio of terephthalic acid to isophthalic acid of 82:18(manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.6 dl/g,Tg: 58° C., Tc: 210° C., Tm: 215° C., Ge content: 10 ppm

(2) PET/I (10): Ethylenephthalate-ethyleneisophthalate copolymerizedresin with a ratio of terephthalic acid to isophthalic acid of 90:10(IP121B manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.6dl/g, Tg: 70° C., Tc: 170° C., Tm: 230° C., Ge content: 10 ppm

(3) PET/I(5): Ethylenephthalate-ethyleneisophthalate copolymerized resinwith a ratio of terephthalic acid to isophthalic acid of 95:5(manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.62 dl/g,Tg: 72° C., Tc: 156° C.; Tm: 255° C., Ge content: 20 ppm

(4) PET/I(2): Ethylenephthalate-ethyleneisophthalate copolymerized resinwith a ratio of terephthalic acid to isophthalic acid of 98:2(manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.6 dl/g,Tg: 68° C., Tc: 150° C., Tm: 250° C., Ge content: 10 ppm

(5) PET: Homopolyethylene phthalate resin (EFG10 manufactured by KaneboGohsen, Ltd.), intrinsic viscosity: 0.62 dl/g, Tg: 72° C., Tc: 150° C.,Tm: 255° C., Ge content: 20 ppm

2. Modified Polyolefin Resin with Group Derived from Carboxylic Acid

(1) EM1: Polymethyl methacrylate-(ethylene-ethyl acrylate copolymer)graft copolymer (Modiper A5200 manufactured by NOF Corp.), weight ratioof functional group derived from carboxylic acid: 21 wt %,glass-transition temperature: −30° C. or lower

(2) EM2: Polymethyl methacrylate-(ethylene-ethyl acrylate-maleicanhydride copolymer) graft copolymer (Modiper A8200 manufactured by NOFCorp.), weight ratio of functional group derived from carboxylic acid:18 wt %, glass-transition temperature: −30° C. or lower

(3) EM3: Ethylene-ethyl acrylate-maleic anhydride copolymer (BondineHX8290 manufactured by Sumitomo Chemical Co., Ltd.), weight ratio offunctional group derived from carboxylic acid: 11 wt %, glass-transitiontemperature: −30° C. or lower

(4) EM4: Ethylene-methacrylic acid copolymer (Nucrel N1560 manufacturedby Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functionalgroup derived from carboxylic acid: 8 wt %, glass-transitiontemperature: −30° C. or lower

(5) EM5: 50% Zn neutralized substance of ethylene-methacrylic acidcopolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical, Co.,Ltd. neutralized partially by Zn), weight ratio of functional groupderived from carboxylic acid: 7 wt %, glass-transition temperature: −30°C. or lower

(6) EM6: 70% Zn neutralized substance of ethylene-methacrylic acidcopolymer (Nucrel N1035 manufactured by Mitsui-DuPont Polychemical Co.,Ltd. neutralized partially by Zn), weight ratio of functional groupderived from carboxylic acid: 5 wt %, glass-transition temperature: −30°C. or lower

(7) EM7: Ethylene-methacrylic acid copolymer (Nucrel N0200H manufacturedby Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functionalgroup-derived from carboxylic acid: 1 wt %, glass-transitiontemperature: −30° C. or lower

(8) EM8: Polystyrene-(ethylene-ethyl acrylate copolymer) graft copolymer(Modiper A5100 manufactured by NOF Corp.), weight ratio of functionalgroup derived from carboxylic acid: 6 wt %, glass-transitiontemperature: 20° C.,

-   -   (9) EPR: Ethylene-propylene rubber (EP07P manufactured by JSR        Corp.), weight ratio of functional group derived from carboxylic        acid: 0 wt %, glass-transition temperature: −30° C. or lower

Pelletized modified polyolefin resin with group derived from carboxylicacid, which was a starting raw material, was mixed with polyester resinin a blending ratio given in comparative example 14 in Table 1, themixed resin was melted and kneaded at 260° C. by using a one-axisextruding machine, and the mixed resin of modified polyolefin resin andpolyester resin was extruded from a T die, by which a resin film with athickness of 25 μm was manufactured.

For the grain diameter of modified polyolefin resin dispersed in resinfilm, polyester resin in the surface layer was etched by alkalineaqueous solution and modified polyolefin grains were caused to remain,the larger diameter and shorter diameter thereof were measured one byone, and the grain diameter (in terms of equivalent sphere) wascalculated, by which the volume ratio, i.e., the number of grains in thefilm with one side of 10 μm was determined. Also, various temperaturesin the tables were measured by a method using the aforementioned DSC.

As a metal sheet, a tin-free steel (hereinafter abbreviated to TFS) witha thickness of 0.18 mm for thin-wall deep drawn can and 0.23 mm for DIcan, which had a degree of temper of DR9, metallic chromium layer of 80mg/m², and chromium oxide layer of 15 mg/m² (metallic chromiumconversion), was used, by which a resin laminated metal sheet wasobtained by a thermo-compression bonding method in which the resin filmobtained as described above was hot-pressed on both surfaces of themetal sheet heated by an induction heating system, and then thelaminated metal sheet was rapidly cooled in water. The metal sheettemperature at the laminating time (laminating temperature) is given inTables 3 and 4.

For the plane orientation coefficient of resin laminated metal sheet,the refractive index was measured by using Abbe's refractometer. Inmeasuring, the light source was a sodium/D ray, the intermediatesolution was methylene iodide, and the temperature was 25° C. Then, therefractive index Nx in the lengthwise direction of metal sheet on thefilm surface, the refractive index Ny in the widthwise direction ofmetal sheet on the film surface, and the refractive index Nz in the filmthickness direction were determined, and the plane orientationcoefficient Ns was calculated by the following equation.Plane orientation coefficient (Ns)=(Nx+Ny)/2−Nz

Furthermore, the resin laminated metal sheet obtained as described abovewas formed into a can, and subjected to straightening heat treatment tomanufacture a sample can. The formability, impact resistance, adhesionafter forming, and adhesion after heating of film of manufactured canbody were investigated.

The following is a detailed description of the investigation method.

1. Evaluation by Thickness-decreasing Deep Drawing

For a resin laminated metal sheet using a TFS with a thickness of 0.18mm, a thin-wall deep drawn can was manufactured by the method describedbelow, and the propriety of thin-wall deep drawn can was investigated.

Can Manufacturing

A resin laminated metal sheet was subjected to first-stage drawing andredrawing under the following conditions, by which a thin-wall deepdrawn can was obtained.

-   First-stage drawing    -   Blank diameter . . . 150 to 160 mm    -   First-stage drawing . . . drawing-ratio: 1.65-   Redrawing    -   Primary redrawing . . . drawing ratio: 1.25    -   Secondary redrawing . . . drawing ratio: 1.25    -   Radius of curvature of die corner in redrawing process . . . 0.4        mm    -   Load for pressing wrinkle at the time of redrawing . . . 39227N        (4000 kg)-   Average thickness decreasing percentage of can sidewall    -   40 to 55% with respect to thickness of resin laminated metal        sheet before forming        1-2 Straightening Heat Treatment

Forming strain of film caused by can manufacturing was removed bykeeping the can in a thermal environment of film melting point minus 15°C. for 30 seconds and then by rapidly cooling it.

1-3 Evaluation of Propriety of Thin-wall Deep Drawn Can

(1) Formability

Evaluation was made as described below by the limit of capability formanufacturing can without film failure. Grades not lower than ◯ markedgrade are acceptable.

-   Limit of forming (thickness decreasing percentage): Grade-   Incapable of forming at thickness decreasing percentage of 40%:    (Inferior)-   Capable of forming up to thickness decreasing percentage of 40%-   Capable of forming up to thickness decreasing percentage of 45%-   Capable of forming up to thickness decreasing percentage of 50%-   Capable of forming up to thickness decreasing percentage of 55%:    (Superior)    (2) Evaluation of Room-temperature and Low-temperature Impact    Resistance

A can body (thickness decreasing percentage: 50%) subjected tostraightening heat treatment was necked, and the can body was filledwith distilled water. After a lid was installed and tightened, an ironball of 0.5 kg was dropped from a height of 30 cm to give a shock to thecan bottom. Thereafter, the lid was opened, and 1% salt water was pouredin the can so that a portion that had suffered shock was immersed. Afterimmersion for five minutes, a load of 6 V was applied across a platinumelectrode immersed in the liquid and a can metal portion, and thecurrent value after five minutes was read, by which evaluation was madeas described below. The same tests were conducted at room temperature of20° C. and at a temperature of 0° C. The former test was for evaluatingroom-temperature impact resistance, and the latter test was forevaluating low-temperature impact resistance. Grades not lower than ◯marked grade are acceptable.

(Evaluation of Room-temperature Impact Resistance)

Test Result: Grade

-   Current value not lower than 30 mA: (Inferior)-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA-   Current value not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA: (Superior)    (Evaluation of Low-temperature Impact Resistance)    Test Result: Grade-   Current value not lower than 30 mA: (Inferior)-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA-   Current value not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA: (Superior)    (3) Adhesion After Forming

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was immersed in aqueous solutioncontaining 1.5 wt % citric acid and 1.5 wt % sodium chloride for 24hours. Thereafter, the peeling length of resin in the can end portionwas observed, and evaluation was made as described below. Grades notlower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling length longer than 10 mm (Inferior)-   Peeling length longer than 5 mm and not longer than 10 mm-   Peeling length longer than 2 mm and not longer than 5 mm-   Peeling length not longer than 2 mm-   No peeling: (Superior)    (4) Adhesion After Heating

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was heated without content therein at210° C. for 10 minutes in an oven. Thereafter, the degree of peeling ofresin in the can end portion was observed, and evaluation was made asdescribed below. Grades not lower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling percentage higher than 10%: (Inferior)-   Peeling percentage higher than 5% and not higher than 10%-   Peeling percentage higher than 2% and not higher than 5%-   Peeling percentage not higher than 2%-   No peeling: (Superior)    2. Evaluation by Drawing and Ironing (DI Forming)

For a resin laminated metal sheet using a TFS with a thickness of 0.23mm, a DI can was manufactured by the method described below, and thepropriety of DI can was investigated.

2-1 Can Manufacturing

A resin laminated metal sheet was drawn and ironed under the followingconditions, by which a DI can was obtained.

-   First-stage drawing    -   Blank diameter: 150 mm    -   Drawing ratio: 1.6-   Second-stage drawing    -   Drawing ratio: 1.25-   Ironing    -   Ironing punch diameter: 3-stage ironing 65.8 mm dia-   Total ironing percentage of can sidewall    -   55 to 70% with respect to thickness of resin laminated metal        sheet before forming        2-2 Straightening Heat Treatment

Forming strain of film caused by can manufacturing was removed bykeeping the can in a thermal environment of film melting point minus 15°C. for 30 seconds and then by rapidly cooling it.

2-3 Evaluation of Propriety of DI Can

(1) Formability

Evaluation was made as described below by the limit of capability formanufacturing can without film failure. Grades not lower than ◯ markedgrade are acceptable.

Limit of forming (total ironing percentage): Grade

-   Incapable of forming at total ironing percentage of 55%: (Inferior)-   Capable of forming up to total ironing percentage of 55%-   Capable of forming up to total ironing percentage of 60%-   Capable of forming up to total ironing percentage of 65%-   Capable of forming up to total ironing percentage of 70%: (Superior)    (2) Evaluation of Room-temperature and Low-temperature Impact    Resistance

A can body (total ironing percentage: 65%) subjected to straighteningheat treatment was necked, and the can body was filled with distilledwater. After a lid was installed and tightened, an iron ball of 0.5 kgwas dropped from a height of 25 cm to give a shock to the can bottom.Thereafter, the lid was opened, and 1% salt water was poured in the canso that a portion that had suffered shock was immersed. After immersionfor five minutes, a load of 6 V was applied across a platinum electrodeimmersed in the liquid and a can metal portion, and the current valueafter five minutes was read, by which evaluation was made as describedbelow. The same tests were conducted at room temperature of 20° C. andat a temperature of 0° C. The former test was for evaluatingroom-temperature impact resistance, and the latter test was forevaluating low-temperature impact resistance. Grades not lower than ◯marked grade are acceptable.

(Evaluation of Room-temperature Impact Resistance)

Test Result: Grade

-   Current value not lower than 30 mA: (Inferior)-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA-   Current value not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA: (Superior)    (Evaluation of Low-temperature Impact Resistance)    Test Result: Grade-   Current value not lower than 30 mA: (Inferior)-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA-   Current value not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA: (Superior)    (3) Adhesion After Forming

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was immersed in aqueous solutioncontaining 1.5 wt % citric acid and 1.5 wt % sodium chloride for fivehours. Thereafter, the peeling length of resin in the can end portionwas observed, and evaluation was made as described below. Grades notlower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling length longer than 10 mm: (Inferior)-   Peeling length longer than 5 mm and not longer than 10 mm-   Peeling length longer than 2 mm and not longer than 5 mm-   Peeling length not longer than 2 mm-   No peeling: (Superior)    (4) Adhesion After Heating

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was heated without content therein at210° C. for 10 minutes in an oven. Thereafter, the degree of peeling ofresin in the can end portion was observed, and evaluation was made asdescribed below. Grades not lower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling percentage higher than 10%: (Inferior)-   Peeling percentage higher than 5% and not higher than 10%-   Peeling percentage higher than 2% and not higher than 5%-   Peeling percentage not higher than 2%-   No peeling: (Superior)    The investigation results are given in Tables 3 and 4.

From Tables 1 to 4, the following facts are found for either can type.

Invention examples 1 to 5 are films in which modified polyolefin resinspecified in the present invention is dispersed in polyester resin inwhich the copolymerization ratio of ethylene terephthalate and ethyleneisophthalate is changed variously, and invention examples 35 to 39 inwhich the films are laminated under the laminating conditions of thepresent invention exhibit high formability, impact resistance, andadhesion. Also, invention example 38 in which the film of inventionexample 4 using polyester resin containing a small amount of isophthalicacid is laminated and invention example 39 in which the film ofinvention example 5 using homopolyethylene terephthalate is laminatedhave a tendency toward deteriorated formability and adhesion, butprovide high performance as a whole. Also, invention example 35 in whichthe film of invention example 1 using polyester resin containing a highamount of isophthalic acid is laminated has a tendency towarddeteriorated adhesion after heating because of a slightly low meltingpoint, but provides high performance as a whole. Further, inventionexamples 33 and 34 are films in which polyester resins with differentcopolymerization ratio of two types are mixed in the range of thepresent invention, and invention examples 67 and 68 in which the filmsare laminated under the laminating conditions of the present inventionhave a tendency toward slightly deteriorated formability, but exhibithigh formability, impact resistance, and adhesion. On the other hand,comparative examples 1 to 6 are examples of films in which polyolefinresin is not contained in polyester resin in which the copolymerizationratio of ethylene terephthalate and ethylene isophthalate is changedvariously. Comparative examples 15 to 20 in which these films arelaminated especially have a low level of impact resistance.

Invention examples 6 to 10 are mixed resins in which various polyolefinresins are dispersed in polyester resin, and invention examples 40 to 44in which the mixed resins are laminated exhibit high formability, impactresistance, and adhesion. However, invention example 40 in which thefilm of invention example 6 using polyolefin resin with a slightly highpercentage of functional group derived from carboxylic acid is laminatedand invention example 44 in which the film of invention example 10 usingpolyolefin resin having a slightly high glass-transition temperature islaminated have a tendency toward slightly deteriorated low-temperatureimpact resistance. On the other hand, comparative examples 11 to 13 aremixed resins in which polyolefin resin containing a functional groupderived from carboxylic acid whose percentage deviates from the range ofthe present invention is dispersed in polyester resin, and comparativeexamples 25 to 27 in which these mixed resins are laminated haveinferior formability and impact resistance.

Comparative example 14 is a film in which modified polyolefin resin withgroup derived from carboxylic acid and polyester resin are simply mixedwith each other, and comparative example 28 in which this film islaminated has greatly deteriorated formability and impact resistancebecause modified polyolefin resin is not dispersed in polyester resin ina fine granular form.

Invention examples 11 to 18 are films in which the blending ratio anddispersion state of modified polyolefin resin in polyester resin arechanged variously in the range of the present invention, and inventionexamples 45 to 52 in which the films are laminated under the laminatingconditions of the present invention exhibit high formability, impactresistance, and adhesion. However, invention example 45 in which thefilm of invention example 11 containing a small amount of dispersedmodified polyolefin resin is laminated and invention example 51 in whichthe film of invention example 17 having a very large number of grains ofmodified polyolefin resin is laminated have a tendency toward slightlydeteriorated low-temperature impact resistance.

On the other hand, comparative examples 7 to 10 are films in which theblending ratio of modified polyolefin resin in polyester resin does notmeet the requirement of the present invention, and comparative examples21 to 24 in which the films are laminated under the laminatingconditions of the present invention have greatly deterioratedformability and impact resistance. Comparative examples 21 and 22 inwhich the films of comparative examples 7 and 8 containing a smallamount of dispersed modified polyolefin resin are laminated have greatlydeteriorated room-temperature impact resistance, and comparativeexamples 23 and 24 in which the films of comparative examples 9 and 10containing a large amount of modified polyolefin resin are laminatedhave greatly deteriorated formability.

Invention examples 19 to 23 are films in which titanium dioxide pigmentis mixed with a mixed resin of modified polyolefin resin and polyesterresin, and invention examples 53 to 57 in which the films are laminatedunder the laminating conditions of the present invention exhibit highformability, impact resistance, and adhesion, and also provide a whiteuniform color tone. However, invention example 53 in which the film ofinvention example 19 in which the added amount of pigment is smallerthan a desired range is laminated has slightly insufficient opacifyingproperty of color tone. On the other hand, invention example 57 in whichthe film of invention example 23 in which the added amount of pigment islarger than a desired range is laminated has slightly deterioratedformability.

Invention examples 24 to 28 are films in which the thickness thereof ischanged in the range of the present invention, and invention examples 58to 62 in which the films are laminated under the laminating conditionsof the present invention exhibit high formability, impact resistance,and adhesion. Invention examples 24 and 28 are films in which thethickness thereof exceeds the desired range of the present invention,and invention examples 58 and 62 in which the films are laminated haveslightly lower formability and impact resistance than the case ofdesired film thickness.

Invention examples 36 and 69 to 72 are films obtained by changing thelaminating conditions of the film of invention example 2 in the range ofthe present invention. If the conditions are within the range of thepresent invention, high formability, impact resistance, and adhesion areexhibited regardless of the laminating temperature. On the other hand,in comparative example 30, the film of invention example 2 was laminatedunder conditions lower than the lower limit of laminating temperaturerange of the present invention, so that the film did not adhere to asteel sheet, and therefore evaluation could not be made. On the otherhand, in comparative example 29, the film of invention example 2 waslaminated under conditions exceeding the upper limit of laminatingtemperature range of the present invention, so that the film fused to alaminate roll, and therefore evaluation could not be made.

Invention examples 29 to 31 are films in which a lubricant, free radicalinhibitor, and compatibilizing agent are mixed, respectively, in a mixedresin of modified polyolefin resin and polyester resin of the presentinvention, and invention examples 63 to 65 in which the films arelaminated under the laminating conditions of the present inventionexhibit high formability, impact resistance, and adhesion. Further,invention examples 63 to 65 also have lubricity, free radicaldeterioration resistance, and compatibility depending on the function ofadded additive, and in particular, invention example 65 exhibitsexcellent low-temperature impact resistance.

Invention example 32 is a film of the present invention that ismanufactured by the two-axis stretching method, and invention examples66 and 73 in which the film is laminated exhibit high performance.Invention example 73, which has a plane orientation coefficient of0.015, exhibits a slightly deteriorated formability. However, in thelow-temperature impact resistance test, it was verified that theformability is slightly higher than the case of low plane orientationcoefficient. Invention example 66, which has a plane orientationcoefficient in the range of the present invention, exhibits very highformability and impact resistance.

TABLE 1 Polyolefin resin Weight Volume Number of percentage Blend-percentage grains with of functional ing of grains diameter of groupderived ratio in with 0.1 to 5 μm Film Polyester resin Pigment fromentire diameter of in cube with Sample thickness Resin Content Resincarboxylic Tg resin 0.1 to 5 μm one side of film (μm) type Additive Kind*1) type acid (wt %)  (° C.) (wt %) (vol %) 10 μm (grains) StretchingInvention 25 PET/I(18) None None 0 EM4 8 <−30 15 12 2000 Non- example 1stretched Invention 25 PET/I(10) None None 0 EM4 8 <−30 15 12 2000 Non-example 2 stretched Invention 25 PET/I(5) None None 0 EM4 8 <−30 15 122000 Non- example 3 stretched Invention 25 PET/I(2) None None 0 EM4 8<−30 15 12 2000 Non- example 4 stretched Invention 25 PET None None 0EM4 8 <−30 15 12 2000 Non- example 5 stretched Invention 25 PET/I(10)None None 0 EM2 18 <−30 15 13 500 Non- example 6 stretched Invention 25PET/I(10) None None 0 EM4 8 <−30 15 12 2000 Non- example 7 stretchedInvention 25 PET/I(10) None None 0 EM5 7 <−30 15 12 2000 Non- example 8stretched Invention 25 PET/I(10) None None 0 EM6 5 <−30 15 12 2000 Non-example 9 stretched Invention 25 PET/I(10) None None 0 EM8 6     20 1512 2000 Non- example 10 stretched Invention 25 PET/I(10) None None 0 EM311 <−30 5 3 3 Non- example 11 stretched Invention 25 PET/I(10) None None0 EM3 11 <−30 5 5 70 Non- example 12 stretched Invention 25 PET/I(10)None None 0 EM3 11 <−30 10 8 30 Non- example 13 stretched Invention 25PET/I(10) None None 0 EM3 11 <−30 10 10 250 Non- example 14 stretchedInvention 25 PET/I(10) None None 0 EM3 11 <−30 15 15 500 Non- example 15stretched Invention 25 PET/I(10) None None 0 EM3 11 <−30 15 18 20000Non- example 16 stretched Invention 25 PET/I(10) None None 0 EM3 11 <−3020 22 200000 Non- example 17 stretched Invention 25 PET/I(10) None None0 EM3 11 <−30 25 20 8000 Non- example 18 stretched Invention 25PET/I(10) None TiO₂ 3 EM5 7 <−30 15 12 2000 Non- example 19 stretchedInvention 25 PET/I(10) None TiO₂ 7 EM5 7 <−30 15 12 2000 Non- example 20stretched Invention 25 PET/I(10) None TiO₂ 15 EM5 7 <−30 15 12 2000 Non-example 21 stretched Invention 25 PET/I(10) None TiO₂ 30 EM5 7 <−30 1512 2000 Non- example 22 stretched Invention 25 PET/I(10) None TiO₂ 50EM5 7 <−30 15 12 2000 Non- example 23 stretched Invention 5 PET/I(10)None None 0 EM6 5 <−30 15 12 2000 Non- example 24 stretched *1) Pigmentcontent means weight percentage (wt %) of pigment with respect to totalfilm amount of entire resin and pigment.

TABLE 2 Polyolefin resin Weight Volume Number of percentage Blend-percentage grains with of functional ing of grains diameter of Filmgroup derived ratio in with 0.1 to 5 μm thick- Polyester resin Pigmentfrom entire diameter of in cube with Sample ness Resin Content Resincarboxylic Tg resin 0.1 to 5 μm one side of film (μm) type Additive Kind*1) type acid (wt %)  (° C.) (wt %) 0.2 (vol %) 10 μm (grains)Stretching Invention 15 PET/I(10) None None 0 EM6 5 <−30 15 12 2000 Non-example 25 stretched Invention 20 PET/I(10) None None 0 EM6 5 <−30 15 122000 Non- example 26 stretched Invention 40 PET/I(10) None None 0 EM6 5<−30 15 12 2000 Non- example 27 stretched Invention 55 PET/I(10) *2)None 0 EM6 5 <−30 15 12 2000 Non- example 28 0.3 wt % stretchedInvention 25 PET/I(10) *3) None 0 EM3 11 <−30 15 12 2000 Non- example 290.1 wt % stretched Invention 25 PET/I(10) *4) None 0 EM3 11 <−30 15 132000 Non- example 30 3 wt % stretched Invention 25 PET/I(10) None None 0EM3 11 <−30 15 12 2000 Non- example 31 stretched Invention 25 PET/I(10)None None 0 EM4 8 <−30 15 12 2000 Two-axis example 32 stretchedInvention 25 PET70% + None None 0 EM4 8 <−30 15 12 2000 Non- example 33PET/ stretched I(10)30% Invention 25 PET40% + None None 0 EM4 8 <−30 1512 2000 Non- example 34 PET/ stretched I(18)60% Comparative 25 PET/I(18)None None 0 None — — 0 0 0 Non- example 1 stretched Comparative 25PET/I(10) None None 0 None — — 0 0 0 Non- example 2 stretchedComparative 25 PET/I(10) None None 0 None — — 0 0 0 Two-axis example 3stretched Comparative 25 PET/I(5) None None 0 None — — 0 0 0 Non-example 4 stretched Comparative 25 PET/I(2) None None 0 None — — 0 0 0Non- example 5 stretched Comparative 25 PET None None 0 None — — 0 0 0Non- example 6 stretched Comparative 25 PET/I(10) None None 0 EM3 11<−30 2 2 3 Non- example 7 stretched Comparative 25 PET/I(10) None None 0EM3 11 <−30 2 2 45 Non- example 8 stretched Comparative 25 PET/I(10)None None 0 EM3 11 <−30 35 28 15000 Non- example 9 stretched Comparative25 PET/I(10) None None 0 EM3 11 <−30 35 28 120000 Non- example 10stretched Comparative 25 PET/I(10) None None 0 EM1 21 <−30 15 14 40 Non-example 11 stretched Comparative 25 PET/I(10) None None 0 EM7 1 <−30 153 20 Non- example 12 stretched Comparative 25 PET/I(10) None None 0 EPR0 <−30 15 1 5 Non- example 13 stretched Comparative 25 PET/I(10) NoneNone 0 EM5 7 <−30 15 Not Not dispersed Non- example 14 dispersed in infine grains stretched fine grains *1) Pigment content means weightpercentage (wt %) of pigment with respect to total film amount of entireresin and pigment. *2) Silicone of lubricant is added by 3 weight partto 100 weight part of mixed resin. *3) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane of free radicalinhibitor is added by 0.1 weight part to 100 weight part of mixed resin.*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) ofcompatibilizing agent is added by 3 weight part to 100 weight part ofmixed resin.

TABLE 3 Melting Thin-wall deep drawn can Drawn and ironed can (DI can)point of Impact Impact Laminated polyester Plane resistance Impactresistance Impact metal Sample resin Laminating orientation (roomresistance Adhesion after Adhesion after (room resistance Adhesion afterAdhesion after sheet film (° C.) temp. (° C.) coefficient Formabilitytemp.) (low temp.) forming heating Formability temp.) (low temp.)forming heating Invention Invention 215 200 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ◯example example 35 1 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚example example 36 2 Invention Invention 255 230 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚example example 37 3 Invention Invention 250 225 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚ ◯ ◯example example 38 4 Invention Invention 255 230 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚ ◯ ◯example example 39 5 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ◯ ◯ ⊚ ⊚example example 40 6 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚example example 41 7 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚example example 42 8 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚example example 43 9 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ◯ ◯ ⊚ ⊚example example 44 10 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ◯ ◯ ◯ ⊚example example 45 11 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ◯ ⊚ ⊚ ⊚example example 46 12 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ◯ ⊚ ⊚ ⊚example example 47 13 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚⊚ example example 48 14 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ example example 49 15 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ◯ ⊚⊚ ⊚ example example 50 16 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ◯ ◯⊚ ⊚ example example 51 17 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚ example example 52 18 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ example example 53 19 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚⊚ ⊚ ⊚⊚ ⊚ ⊚ example example 54 20 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ example example 55 21 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ example example 56 22 Invention Invention 230 210 0 ⊚ ⊚⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚ ◯ ⊚ example example 57 23 Invention Invention 230 210 0 ⊚⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚ ⊚ ⊚ example example 58 24

TABLE 4 Thin-wall deep drawn can Drawn and ironed can (DI can) MeltingImpact Impact Impact Impact Laminated point of Plane resistanceresistance resistance resistance metal Sample polyester Laminatingorientation (room (low Adhesion after Adhesion after (room (low Adhesionafter Adhesion after sheet film resin (° C.) temp. (° C.) coefficientFormability temp.) temp.) forming heating Formability temp.) temp.)forming heating Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚example 59 example 25 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚⊚ example 60 example 26 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ example 61 example 27 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚ ⊚ example 62 example 28 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚ example 63 example 29 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ example 64 example 30 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚⊚ ⊚ ⊚⊚⊚ ⊚ ⊚ example 65 example 31 Invention Invention 230 210 0.005 ⊚ ⊚⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚ example 66 example 32 Invention Invention 255 230 0 ⊚⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚ ⊚ ⊚ example 67 example 33 Invention Invention 255 230 0⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚ ⊚ ◯ example 68 example 34 Invention Invention 230 2550 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚ ⊚ ⊚ example 69 example 2 Invention Invention 230 2300 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ example 70 example 2 Invention Invention 230 1900 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ example 71 example 2 Invention Invention 230 1700 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ◯ ◯ example example 72 2 Invention Invention 230 2000.015 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚⊚ ⊚ ⊚ example 73 example 32 ComparativeComparative 215 200 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ Δ XX Δ Δ Δ example example 15 1Comparative Comparative 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ Δ XX Δ Δ ◯ example 16example 2 Comparative Comparative 255 225 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ X XX Δ Δ ◯example example 17 3 Comparative Comparative 250 230 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ Δ XX ΔΔ ◯ example 18 example 4 Comparative Comparative 255 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ XXX Δ X ◯ example example 19 5 Comparative Comparative 230 210 0 ⊚ ⊚ ⊚⊚ ⊚⊚ XX XX Δ XX Δ example 20 example 6 Comparative Comparative 230 210 0 ⊚⊚ ⊚⊚ ⊚ ⊚ ◯ XX Δ Δ ◯ example example 21 7 Comparative Comparative 230 2100 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ X Δ ◯ ⊚ example 22 example 8 Comparative Comparative 230210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ X ◯ Δ X ◯ example example 23 9 Comparative Comparative230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ XX ◯ Δ XX ◯ example 24 example 10 ComparativeComparative 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ X ◯ Δ ◯ ◯ example example 25 11Comparative Comparative 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ Δ X Δ ◯ Δ example 26example 12 Comparative Comparative 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ X XX Δ X Xexample example 27 13 Comparative Comparative 230 210 0 ⊚ ⊚ ⊚⊚ ⊚ ⊚ XX XXΔ XX Δ example 28 example 14 Comparative Invention 230 265 — — — — — — —— — — — example example 29 2 Comparative Invention 230 150 — — — — — — —— — — — example 30 example 2

Example 2

Modified polyolefin resin with group derived from carboxylic acid havinga primary grain diameter of 0.3 μm, which was a starting raw material,was cold blended with polyester resin in a blending ratio given inTables 5 and 6 by using a tumbler blender, and then the blended resinwas melted and kneaded at 260° C. by using a two-axis extruding machine,by which a raw material pellet of polyester resin in which modifiedpolyolefin resin was dispersed was obtained. In the tables, the resintype corresponding to the symbol of resin type of polyester resin andresin type of polyolefin resin is the same as that described in Example1.

As a metal sheet, as in Example 1, a tin-free steel (hereinafterabbreviated to TFS) with a thickness of 0.18 mm for thin-wall deep drawncan and 0.23 mm for DI can, which had a degree of temper of DR9,metallic chromium layer of 80 mg/m², and chromium oxide layer of 15mg/m² (metallic chromium conversion), was used, by which a both-sideresin laminated metal sheet was obtained by a method in which the rawmaterial resin pellet was inserted in a one-axis extruding machine,molten resin was extruded directly from a T die onto one surface of themetal sheet, the extruded resin was once cooled while being heldadherently between two rolls, and immediately after the resin waslaminated on the opposite surface in the same manner, the resinlaminated metal sheet was cooled rapidly in water. The temperature ofmetal sheet at the laminating time was 50° C. The lip opening width of Tdie was adjusted so that the thickness of resin film was 6 to 55 μm. Thetype of sample resin and the resin-melting temperature at the laminatingtime are given in Tables 7 and 8. The used polyester resin and modifiedpolyolefin resin with group derived from carboxylic acid are the same asthose used in Example 1.

Pelletized modified polyolefin resin with group derived from carboxylicacid, which was a starting raw material, was mixed with polyester resinin a blending ratio given in comparative example 43 in Table 6, themixed resin was melted and kneaded at 260° C. by using a one-axisextruding machine, and the obtained mixed resin of modified polyolefinresin and polyester resin was extruded from a T die, by which the resinthat had been directly extruded to a thickness of 25 μm was laminated tothe TFS.

All of the grain diameter of modified polyolefin resin dispersed inresin film, various temperatures in the table, and the method formeasuring the plane orientation coefficient of laminated metal sheet arethe same as those in Example 1. As in Example 1, a thin-wall deep drawncan or a DI can was manufactured from the laminated metal sheet obtainedas described above, and the can was subjected to straightening heattreatment to manufacture a sample can. The formability, impactresistance, and adhesion of film of the manufactured can body wereinvestigated as in Example 1.

The investigation results are given in Tables 7 and 8.

From Tables 5 to 8, the following facts are found for either can type.

Invention examples 74 to 82 are films which are formed by dispersingmodified polyolefin resin specified in the present invention inpolyester resin in which the copolymerization ratio of ethyleneterephthalate and ethylene isophthalate is changed variously, andexhibit high formability, impact resistance, and adhesion. Also,invention example 81 using polyester resin containing a small amount ofisophthalic acid and invention example 82 using homopolyethyleneterephthalate have a tendency toward deteriorated formability andadhesion, but provide high performance as a whole. Also, inventionexample 74 using polyester resin containing a large amount ofisophthalic acid has a tendency toward deteriorated adhesion afterheating because of slightly low melting point, but provide highperformance as a whole. Further, invention examples 109 and 110 areresins in which polyester resins with different copolymerization ratioof two types are mixed in the range of the present invention, and have atendency toward slightly deteriorated formability, but exhibit highformability, impact resistance, and adhesion. On the other hand,comparative examples 31 to 35 are examples of resins in which polyolefinresin is not contained in polyester resin in which the copolymerizationratio of ethylene terephthalate and ethylene isophthalate is changedvariously, and especially have a low level of impact resistance.

Invention examples 83 to 87 are examples of mixed resins in whichvarious polyolefin resins are dispersed in polyester resin, and exhibithigh formability, impact resistance, and adhesion. However, inventionexample 83 using polyolefin resin with a slightly high percentage offunctional group derived from carboxylic acid and invention example 87using polyolefin resin with a slightly high glass-transition temperaturehave a tendency toward slightly deteriorated low-temperature impactresistance. On the other hand, comparative examples 40 to 42 are mixedresins in which polyolefin resin containing a functional group derivedfrom carboxylic acid whose percentage deviates from the range of thepresent invention is dispersed in polyester resin, and have inferiorformability and impact resistance.

Comparative example 43 is a resin in which modified polyolefin resinwith group derived from carboxylic acid and polyester resin are simplymixed with each other, and has greatly deteriorated formability andimpact resistance because modified polyolefin resin is not dispersed inpolyester resin in a fine granular form.

Invention examples 88 to 95 are resins in which the blending ratio anddispersion state of modified polyolefin resin in polyester resin arechanged variously in the range of the present invention, and exhibithigh formability, impact resistance, and adhesion. However, the resin ofinvention example 88 containing a small amount of dispersed-modifiedpolyolefin resin and the resin of invention example 94 having a verylarge number of grains of modified polyolefin resin have a tendencytoward slightly deteriorated low-temperature impact resistance.

On the other hand, comparative examples 36 to 39 are resins in which theblending ratio of modified polyolefin resin in polyester resin does notmeet requirement of the present invention, and have greatly deterioratedformability and impact resistance. Comparative examples 36 and 37containing a small amount of dispersed modified polyolefin resin havegreatly deteriorated room-temperature impact resistance, and comparativeexamples 38 and 39 containing a large amount of modified polyolefinresin have greatly deteriorated formability.

Invention examples 96 to 100 are resins in which titanium dioxidepigment is mixed with a mixed resin of modified polyolefin resin andpolyester resin, and exhibit high formability, impact resistance, andadhesion, and also provide a white uniform color tone. However,invention example 96 in which the added amount of pigment is smallerthan a desired range has slightly insufficient opacifying property ofcolor tone. On the other hand, invention example 100 in which the addedamount of pigment is larger than a desired range has slightlydeteriorated formability.

Invention examples 101 to 105 are resins in which the thickness thereofis changed in the range of the present invention, and exhibit highformability, impact resistance, and adhesion. Invention examples 101 and105 are resins in which the thickness thereof exceeds the desired rangeof the present invention, and have slightly lower formability and impactresistance than the case of desired film thickness.

Invention examples 75 to 79 are resins obtained by changing theextrusion laminating conditions in the range of the present invention.If the conditions are within the range of the present invention, highformability, impact resistance, and adhesion are exhibited regardless ofthe laminating temperature. Invention example 75 was laminated underconditions lower than the desired lower limit of laminating temperaturerange, and invention example 79 was laminated under conditions exceedingthe desired upper limit of laminating temperature range, so that theseinvention examples have slightly deteriorated formability andtemperature impact resistance.

Invention examples 106 to 108 are resins in which a lubricant, freeradical inhibitor, and compatibilizing agent are mixed, respectively, ina mixed resin of modified polyolefin resin and polyester resin of thepresent invention, and exhibit high formability, impact resistance, andadhesion. Further, invention examples 106 to 108 also have lubricity,free radical deterioration resistance, and compatibility depending onthe function of added additive, and in particular, invention example 108exhibits excellent low-temperature impact resistance.

TABLE 5 Polyolefin resin Weight percentage of Volume percentage Numberof grains with Laminated Polyester resin Pigment functional groupBlending of grains with diameter of 0.1 to metal Resin Addi- ContentResin derived from Tg ratio in entire diameter of 5 μm in cube with onesheet type tive Kind *1) type carboxylic acid (wt %) (° C.) resin (wt %)0.1 to 5 μm (vol %) side of 10 μm (grains) Invention PET/I(18) None None0 EM4 8 <−30 15 14 2500 example 74 Invention PET/I(10) None None 0 EM4 8<−30 15 14 2500 example 75 Invention PET/I(10) None None 0 EM4 8 <−30 1514 2500 example 76 Invention PET/I(10) None None 0 EM4 8 <−30 15 14 2500example 77 Invention PET/I(10) None None 0 EM4 8 <−30 15 14 2500 example78 Invention PET/I(10) None None 0 EM4 8 <−30 15 14 2500 example 79Invention PET/I(5) None None 0 EM4 8 <−30 15 14 2500 example 80Invention PET/I(2) None None 0 EM4     8 <−30 15 14 2500 example 81Invention PET None None 0 EM4 8 <−30 15 14 2500 example 82 InventionPET/I(10) None None 0 EM2 18 <−30 15 15 1000 example 83 InventionPET/I(10) None None 0 EM4 8 <−30 15 14 2500 example 84 InventionPET/I(10) None None 0 EM5 7 <−30 15 14 2500 example 85 InventionPET/I(10) None None 0 EM6 5 <−30 15 14 2500 example 86 InventionPET/I(10) None None 0 EM8 6     20 15 14 2500 example 87 InventionPET/I(10) None None 0 EM3 11 <−30 5 4 4 example 88 Invention PET/I(10)None None 0 EM3 11 <−30 5 8 100 example 89 Invention PET/I(10) None None0 EM3 11 <−30 10 10 50 example 90 Invention PET/I(10) None None 0 EM3 11<−30 10 12 500 example 91 Invention PET/I(10) None None 0 EM3 11 <−30 1518 800 example 92 Invention PET/I(10) None None 0 EM3 11 <−30 15 2022000 example 93 Invention PET/I(10) None None 0 EM3 11 <−30 20 24250000 example 94 Invention PET/I(10) None None 0 EM3 11 <−30 25 2210000 example 95 Invention PET/I(10) None TiO₂ 3 EM5 7 <−30 15 14 2500example 96 Invention PET/I(10) None TiO₂ 7 EM5 7 <−30 15 14 2500 example97 Invention PET/I(10) None TiO₂ 15 EM5 7 <−30 15 14 2500 example 98Invention PET/I(10) None TiO₂ 30 EM5 7 <−30 15 14 2500 example 99Invention PET/I(10) None TiO₂ 50 EM5 7 <−30 15 14 2500 example 100 *1)Pigment content means weight percentage (wt %) of pigment with respectto total film amount of entire resin and pigment.

TABLE 6 Polyolefin resin Blending Volume Weight percentage of ratiopercentage Number of grains with Laminated Polyester resin Pigmentfunctional group in entire of grains with diameter of 0.1 to metal ResinAddi- Content Resin derived from Tg resin diameter of 0.1 5 μm in cubewith one sheet type tive Kind *1) type carboxylic acid (wt %) (° C.) (wt%) to 5 μm (vol %) side of 10 μm (grains) Invention PET/I(10) None None0 EM6 5 <−30 15 14 2500 example 101 Invention PET/I(10) None None 0 EM65 <−30 15 14 2500 example 102 Invention PET/I(10) None None 0 EM6 5 <−3015 14 2500 example 103 Invention PET/I(10) None None 0 EM6 5 <−30 15 142500 example 104 Invention PET/I(10) None None 0 EM6 5 <−30 15 14 2500example 105 Invention PET/I(10) *2) None 0 EM3 11 <−30 15 14 2500example 106 0.3 wt % Invention PET/I(10) *3) None 0 EM3 11 <−30 15 142500 example 107 0.1 wt % Invention PET/I(10) *4) None 0 EM3 11 <−30 1514 2500 example 108 3 wt % Invention PET70% + None None 0 EM4 8 <−30 1514 2500 example 109 PET/ I(10)30% Invention PET40% + None None 0 EM4 8<−30 15 14 2500 example 110 PET/ I(18)60% Comparative PET/I(18) NoneNone 0 None — — 0 0 0 example 31 Comparative PET/I(10) None None 0 None— — 0 0 0 example 32 Comparative PET/I(5) None None 0 None — — 0 0 0example 33 Comparative PET/I(2) None None 0 None — — 0 0 0 example 34Comparative PET None None 0 None — — 0 0 0 example 35 ComparativePET/I(10) None None 0 EM3 11 <−30 2 3 5 example 36 Comparative PET/I(10)None None 0 EM3 11 <−30 2 3 50 example 37 Comparative PET/I(10) NoneNone 0 EM3 11 <−30 35 30 20000 example 38 Comparative PET/I(10) NoneNone 0 EM3 11 <−30 35 30 130000 example 39 Comparative PET/I(10) NoneNone 0 EM1 21 <−30 15 16 50 example 40 Comparative PET/I(10) None None 0EM7 1 <−30 15 4 40 example 41 Comparative PET/I(10) None None 0 EPR 0<−30 15 1 4 example 42 Comparative PET/I(10) None TiO₂ 3 EM5 7 <−30 15Not dispersed in Not dispersed example 43 fine grains in fine grains *1)Pigment content means weight percentage (wt %) of pigment with respectto total film amount of entire resin and pigment. *2) Silicone oflubricant is added by 3 weight part to 100 weight part of mixed resin.*3) Tetrakis-[methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane of free radical inhibitor is added by 0.1 weight part to 100weight part of mixed resin. *4) Bond First 20B (manufactured by SumitomoChemical Co., Ltd.) of compatibilizing agent is added by 3 weight partto 100 weight part of mixed resin.

TABLE 7 Melting point of mixed Thin-wall deep drawn can Drawn and ironedcan (DI can) Laminated resin (melting Melting temp. of Impact ImpactAdhesion Adhesion Impact Impact Adhesion Adhesion metal point ofpolyester mixed resin Resin thickness resistance resistance after afterresistance resistance after after sheet resin) (° C.) (° C.) (μm)Formability (room temp.) (low temp.) forming heating Formability (roomtemp.) (low temp.) forming heating Invention example 74 215 235 25 ⊚ ⊚⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ◯ Invention example 75 230 235 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚ ◯ ⊚Invention example 76 230 240 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ Invention example77 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ Invention example 78 230 265 25 ⊚ ⊚⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ Invention example 79 230 275 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ◯ ◯ ◯ ⊚Invention example 80 255 275 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ Invention example81 250 270 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚ ◯ ◯ Invention example 82 255 275 25 ⊚ ⊚⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚ ◯ ◯ Invention example 83 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ◯ ◯ ⊚ ⊚Invention example 84 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ Invention example85 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ Invention example 86 230 250 25 ⊚ ⊚⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ Invention example 87 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ◯ ◯ ⊚ ⊚Invention example 88 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ◯ ◯ ◯ ⊚ Invention example89 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Invention example 90 230 250 25 ⊚ ⊚⊚⊚ ⊚ ⊚ ⊚ ◯ ⊚ ⊚ ⊚ Invention example 91 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚Invention example 92 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ Invention example93 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ◯ ⊚ ⊚ ⊚ Invention example 94 230 250 25 ⊚ ⊚⊚⊚ ⊚ ⊚ ⊚ ◯ ◯ ⊚ ⊚ Invention example 95 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚Invention example 96 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ Invention example97 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ Invention example 98 230 250 25 ⊚ ⊚⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ Invention example 99 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚Invention example 100 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚ ◯ ⊚ *1) Pigmentcontent means weight percentage (wt %) of pigment with respect to totalfilm amount of entire resin and pigment.

TABLE 8 Melting Drawn and ironed can (DI can) point of mixed Thin-walldeep drawn can Impact Laminated resin (melting Melting temp. of ImpactImpact Adhesion Adhesion resistance Impact Adhesion metal point ofpolyester mixed resin Resin thickness resistance resistance after after(room resistance after Adhesion sheet resin) (° C.) (° C.) (μm)Formability (room temp.) (low temp.) forming heating Formability temp.)(low temp.) forming after heating Invention 230 250 6 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚ ⊚⊚ example 101 Invention 230 250 15 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ example 102Invention 230 250 20 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ example 103 Invention 230 25040 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ example 104 Invention 230 250 55 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚⊚ ⊚ ⊚ example 105 Invention 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ example 106Invention 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ ⊚ example 107 Invention 230 25025 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚ example 108 Invention 255 275 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯⊚ ⊚⊚ ⊚ ⊚ example 109 Invention 255 275 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ ⊚ ⊚⊚ ⊚ ◯ example110 Comparative 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ Δ XX Δ Δ Δ example 31 Comparative255 275 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ Δ XX Δ Δ ◯ example 32 Comparative 250 270 25 ⊚ ⊚⊚⊚ ⊚ ⊚ Δ XX Δ Δ ◯ example 33 Comparative 255 275 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ X XX Δ X◯ example 34 Comparative 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ XX XX Δ XX Δ example 35Comparative 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ XX Δ Δ ◯ example 36 Comparative 230250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ ◯ X Δ ◯ ⊚ example 37 Comparative 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚X Δ Δ X ◯ example 38 Comparative 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ XX Δ Δ XX ◯example 39 Comparative 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ X Δ Δ ◯ ◯ example 40Comparative 230 250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ Δ X Δ ◯ Δ example 41 Comparative 230250 25 ⊚ ⊚ ⊚⊚ ⊚ ⊚ X XX Δ X X example 42 Comparative 230 250 25 ⊚ ⊚ ⊚⊚ ⊚⊚ XX XX Δ XX Δ example 43 *1) Pigment content means weight percentage(wt %) of pigment with respect to total film amount of entire resin andpigment. *2) Silicone of lubricant is added by 3 weight part to 100weight part of mixed resin. *3) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane of free radicalinhibitor is added by 0.1 weight part to 100 weight part of mixed resin.*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) ofcompatibilizing agent is added by 3 weight part to 100 weight part ofmixed resin.

Example 3

As a resin raw material, modified polyolefin resin with group derivedfrom carboxylic acid was cold blended with polyester resin in a blendingratio given in Tables 9 to 12 by using a tumbler blender, and then theblended resin was melted and kneaded at 270° C. by using a two-axisextruding machine, by which a raw material pellet of polyester resin inwhich modified polyolefin resin was dispersed was obtained. The obtainedraw material resin pellet was inserted in a one-axis extruding machine,and was extruded from a multi-manifold type T die while being controlledby the discharge amount of molten resin from the extruding machine, bywhich a resin film with a total thickness of 10 to 50 μm wasmanufactured continuously while being cooled by the surface of arotating metallic roll.

On the other hand, in the case of film of two-layer construction,modified polyolefin resin with group derived from carboxylic acid, whichwas a resin raw material for R1 layer, was cold blended with polyesterresin in a blending ratio given in Tables 9 to 12 by using a tumblerblender, and then the blended resin was melted and kneaded at 270° C. byusing a two-axis extruding machine, by which a raw material pellet ofpolyester resin in which modified polyolefin resin was dispersed wasobtained. The obtained raw material resin pellet was inserted in aone-axis extruding machine, and on the other hand, polyester resincontaining no modified polyolefin resin, which was a resin raw materialfor R0 layer, was inserted in a separate one-axis extruding machine, andeach of molten resins was introduced into a multi-manifold type T dieand extruded in two layers while being controlled by the dischargeamount of molten resin from the extruding machine, by which a resin filmwas manufactured continuously while being cooled by the surface of arotating metallic roll.

The used polyester resin and modified polyolefin resin with groupderived from carboxylic acid were as follows:

1. Polyester Resin

(1) PET: Polyethylene terephthalate resin, intrinsic viscosity: 0.62dl/g

(2) PET/I (10): Isophthalic acid copolymerized resin with a ratio ofterephthalic acid to isophthalic acid of 90:10, intrinsic viscosity: 0.6dl/g

(3) PET/PBT (60): mixed resin with a ratio of polyethylene terephthalateto polybutylene terephthalate of 40:60, intrinsic viscosity: 0.6 dl/g

(4) PET/AD(20): Adipic acid copolymerized polyethylene terephthalatecopolymerized resin with a ratio of terephthalic acid to adipic acid of80:20, intrinsic viscosity: 0.6 dl/g

2. Modified Polyolefin Resin with Group Derived from Carboxylic Acid

(1) EM1: Polymethyl methacrylate-(ethylene-ethyl acrylate copolymer)graft copolymer (Modiper A5200 manufactured by NOF Corp.), weight ratioof functional group derived from carboxylic acid: 21 wt %,glass-transition temperature: −30° C. or lower

(2) EM2: Polymethyl methacrylate-(ethylene-ethyl acrylate-maleicanhydride copolymer) graft copolymer (Modiper A8200 manufactured by NOFCorp.), weight ratio of functional group derived from carboxylic acid:18 wt %, glass-transition temperature: −30° C. or lower

(3) EM3: Ethylene-ethyl acrylate-maleic anhydride copolymer (BondineHX8290 manufactured by Sumitomo Chemical Co., Ltd.), weight ratio offunctional group derived from carboxylic acid: 11 wt %, glass-transitiontemperature: −30° C. or lower

(4) EM4: Ethylene-methacrylic acid copolymer (Nucrel N1560 manufacturedby Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functionalgroup derived from carboxylic acid: 8 wt %, glass-transitiontemperature: −30° C. or lower

(5) EM5: 50% Zn neutralized substance of ethylene-methacrylic acidcopolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical Co.,Ltd. neutralized partially by Zn), weight ratio of functional groupderived from carboxylic acid: 7 wt %, glass-transition temperature: −30°C. or lower

(6) EM6: 60% Zn neutralized substance of ethylene-methacrylic acidcopolymer (Himilan 1557 manufactured by Mitsui-DuPont Polychemical Co.,Ltd.), weight ratio of functional group derived from carboxylic acid: 5wt %, glass-transition temperature: −30° C. or lower

(7) EM7: Ethylene-methacrylic acid copolymer (Nucrel N0200H manufacturedby Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functionalgroup derived from carboxylic acid: 1 wt %, glass-transitiontemperature: −30° C. or lower

(8) EM8: Polystyrene-(ethylene-ethyl acrylate copolymer) graft copolymer(Modiper A5100 manufactured by NOF Corp.), weight ratio of functionalgroup derived from carboxylic acid: 6 wt %, glass-transitiontemperature: 20° C.

(9) EPR: Ethylene-propylene rubber (EP07P manufactured by JSR Corp.),weight ratio of functional group derived from carboxylic acid: 0 wt %,glass-transition temperature: −30° C. or lower

Furthermore, a commercially available resin (Sealer PT4274 manufacturedby Mitsui-DuPont Polychemical Co., Ltd.) that had been pelletized inadvance in a state in which modified polyolefin resin with group derivedfrom carboxylic acid was dispersed in polyester resin, which was used asa resin raw material, was inserted in a one-axis extruding machine inblending ratios shown in invention examples 32 and 36 in Table 11, andwas extruded from a multi-manifold type T die while being controlled bythe discharge amount of molten resin from the extruding machine, bywhich resin films of single layer and two layers were manufacturedcontinuously while being cooled by the surface of a rotating metallicroll.

A resin laminated metal sheet was obtained by a thermo-compressionbonding method in which the resin film obtained as described above washot-pressed on both surfaces of a tin-free steel (hereinafterabbreviated to TFS, thickness: 0.18 mm for thin-wall deep drawn can and0.23 mm for DI can, degree of temper: DR9, metallic chromium layer: 80mg/m², chromium oxide layer: 15 mg/m² (metallic chromium conversion))heated by an induction heating system, and then the laminated metalsheet was rapidly cooled in water. The metal sheet temperature at thelaminating time (laminating temperature) is given in Tables 13 and 14.

The grain diameter of modified polyolefin resin dispersed in R1 layer ofresin film, various temperatures in the table, and the plane orientationcoefficient of resin laminated metal sheet were measured by the samemethod as that in Example 1.

A thin-wall deep drawn can or a DI can was manufactured from thelaminated metal sheet obtained as described above, and the can wassubjected to straightening heat treatment to manufacture a sample can.The formability, impact resistance (room temperature, low temperature),adhesion after forming, adhesion after heating, and flavor property offilm of the manufactured can body were investigated.

The following is a detailed description of the investigation method.

1. Evaluation by Thickness-decreasing Deep Drawing

1-1 Can Manufacturing

A resin laminated metal sheet was subjected to first-stage drawing andredrawing under the following conditions, by which a thin-wall deepdrawn can was obtained.

-   First-stage drawing    -   Blank diameter . . . 150 to 160 mm    -   First-stage drawing . . . drawing ratio: 1.65-   Redrawing    -   Primary redrawing . . . drawing ratio: 1.25    -   Secondary redrawing . . . drawing ratio: 1.25    -   Radius of curvature of die corner in redrawing process . . . .        0.4 mm    -   Load for pressing wrinkle at the time of redrawing . . . 39227N        (4000 kg)-   Average thickness decreasing percentage of can sidewall    -   40 to 55% with respect to thickness of resin laminated metal        sheet before forming        1-2 Straightening Heat Treatment.

Forming strain of film caused by can manufacturing was removed bykeeping the can in a thermal environment of film melting point minus 15°C. for 30 seconds and then by rapidly cooling it.

(1) Formability

Evaluation was made as described below by the limit of capability formanufacturing can without film failure. Grades not lower than ◯ markedgrade are acceptable.

Limit of forming (thickness decreasing percentage): Grade

-   Incapable of forming at thickness decreasing percentage of 40%:    (Inferior)-   Capable of forming up to thickness decreasing percentage of 40%-   Capable of forming up to thickness decreasing percentage of 45%-   Capable of forming up to thickness decreasing percentage of 50%-   Capable of forming up to thickness decreasing percentage of 55%:    (Superior)    (2) Evaluation of Room-temperature and Low-temperature Impact    Resistance

A can body (thickness decreasing percentage: 50%) subjected tostraightening heat treatment was necked, and the can body was filledwith distilled water. After a lid was installed and tightened, an ironball of 0.5 kg was dropped from a height of 30 cm to give a shock to thecan bottom. Thereafter, the lid was opened, and 1% salt water was pouredin the can so that a portion that had suffered shock was immersed. Afterimmersion for five minutes, a load of 6 V was applied across a platinumelectrode immersed in the liquid and a can metal portion, and thecurrent value after five minutes was read, by which evaluation was madeas described below. The same tests were conducted at room temperature of20° C. and at a temperature of 0° C. The former test was for evaluatingroom-temperature impact resistance, and the latter test was forevaluating low-temperature impact resistance. Grades not lower than ◯marked grade are acceptable.

(Evaluation of Room-temperature Impact Resistance)

Test Result: Grade

-   Current value not lower than 30 mA: (Inferior)-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA-   Current value not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA: (Superior)    (Evaluation of Low-temperature Impact Resistance)    Test Result: Grade-   Current value not lower than 50 mA: (Inferior)-   Current value not lower than 30 mA and lower than 50 mA-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA-   Current value not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA: (Superior)    (3) Adhesion after Forming

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was immersed in aqueous solutioncontaining 1.5 wt % citric acid and 1.5 wt % sodium chloride for 24hours. Thereafter, the peeling length of resin in the can end portionwas observed, and evaluation was made as described below. Grades notlower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling length longer than 10 mm: (Inferior)-   Peeling length longer than 5 mm and not longer than 10 mm-   Peeling length longer than 2 mm and not longer than 5 mm-   Peeling length not longer than 2 mm-   No peeling: (Superior)    (4) Adhesion After Heating

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was heated without content therein at210° C. for 10 minutes in an oven. Thereafter, the degree of peeling ofresin in the can end portion was observed, and evaluation was made asdescribed below. Grades not lower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling-percentage higher than 10%: (Inferior)-   Peeling percentage higher than 5% and not higher than 10%-   Peeling percentage higher than 2% and not higher than 5%-   Peeling percentage higher than 0.5% and not higher than 2%-   Peeling percentage not higher than 0.5%-   No peeling: (Superior)    (5) Flavor Property

The internal surface of can body subjected to straightening heattreatment was cleaned, and flavor aqueous solution (d-limonene 20 ppmaqueous solution) was put in the can and left at ordinary temperaturefor 20 days after sealing. Thereafter, the can was unsealed, and aportion expelled by ether immersion was determined by gas chromatographyas adsorption of d-limonene per can, by which flavor property wasevaluated. Grades not lower than ◯ marked-grade are acceptable.

Test Result: Grade

-   Adsorption larger than 200 μg/can: (Inferior)-   Adsorption larger than 100 μg/can and not larger than 200 μg/can-   Adsorption larger than 30 μg/can and not larger than 100 μg/can-   Adsorption larger than 10 μg/can and not larger than 30 μg/can-   Adsorption not larger than 10 μg/can: (Superior)    2. Evaluation by Drawing and Ironing (DI Forming)    2-1 Can Manufacturing

A resin laminated metal sheet was drawn and ironed under the followingconditions, by which a DI can was obtained.

-   First-stage drawing    -   Blank diameter: 150 mm    -   Drawing ratio: 1.6-   Second-stage drawing    -   Drawing ratio: 1.25-   Ironing    -   Ironing punch diameter: 3-stage ironing 65.8 mm dia-   Total ironing percentage of can sidewall    -   55 to 70% with respect to thickness of resin laminated metal        sheet before forming        2-2 Straightening Heat Treatment

Forming strain of film caused by can manufacturing was removed bykeeping the can in a thermal environment of film melting point minus 15°C. for 30 seconds and then by rapidly cooling it.

(1) Formability

Evaluation was made as described below by the limit of capability formanufacturing can without film failure. Grades not lower than ◯ markedgrade are acceptable.

Limit of forming (total ironing percentage): Grade

-   Incapable of forming at total ironing percentage of 55%: (Inferior)-   Capable of forming up to total ironing percentage of 55%-   Capable of forming up to total ironing percentage of 60%-   Capable of forming up to total ironing percentage of 65%-   Capable of forming up to total ironing percentage of 70%: (Superior)    (2) Evaluation of Room-temperature and Low-temperature Impact    Resistance

A can body (total-ironing percentage: 65%) subjected to straighteningheat treatment was necked, and the can body was filled with distilledwater. After a lid was installed and tightened, an iron ball of 0.5 kgwas dropped from a height of 25 cm to give a shock to the can bottom.Thereafter, the lid was opened, and 1% salt water was poured in the canso that a portion that had suffered shock was immersed. After immersionfor five minutes, a load of 6 V was applied across a platinum electrodeimmersed in the liquid and a can metal portion, and the current valueafter five minutes was read, by which evaluation was made as describedbelow. The same tests were conducted at room temperature of 20° C. andat a temperature of 0° C. The former test was for evaluatingroom-temperature impact resistance, and the latter test was forevaluating low-temperature impact resistance. Grades not lower than ◯marked grade are acceptable.

(Evaluation of Room-temperature Impact Resistance)

Test Result: Grade

-   Current value not lower than 30 mA: (Inferior)-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA-   Current value not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA (Superior)    (Evaluation of Low-temperature Impact Resistance)    Test Result: Grade-   Current value not lower than 50 mA: (Inferior)-   Current value not lower than 30 mA and lower than 50 mA-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA Current value    not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA: (Superior)    (3) Adhesion After Forming

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was immersed in aqueous solutioncontaining 1.5 wt % citric acid and 1.5 wt % sodium chloride for fivehours. Thereafter, the peeling length of resin in the can end portionwas observed, and evaluation was made as described below. Grades notlower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling length longer than 10 mm: (Inferior)-   Peeling length longer than 5 mm and not longer than 10 mm-   Peeling length longer than 2 mm and not longer than 5 mm-   Peeling length not longer than 2 mm-   No peeling: (Superior)    (4) Adhesion After Heating

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was heated without content therein at210° C., for 10 minutes in an oven. Thereafter, the degree of peeling ofresin in the can end portion was observed, and evaluation was made asdescribed below. Grades not lower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling percentage higher than 10%: (Inferior)-   Peeling percentage higher than 5% and not higher than 10%-   Peeling percentage higher than 2% and not higher than 5%-   Peeling percentage higher than 0.5% and not higher than 2%-   Peeling percentage not higher than 0.5%-   No peeling: (Superior)    (5) Flavor Property.

The internal surface of can body subjected to straightening heattreatment was cleaned, and flavor aqueous solution (d-limonene 20 ppmaqueous solution) was put in the can and left at ordinary temperaturefor 20 days after sealing. Thereafter, the can was unsealed, and aportion expelled by ether immersion was determined by gas chromatographyas adsorption of d-limonene per can, by which flavor property wasevaluated. Grades not lower than ◯ marked grade are acceptable.

Test Result: Grade

-   Adsorption larger than 200 μg/cane: (Inferior)-   Adsorption larger than 100 μg/can and not larger than 200 μg/can-   Adsorption larger than 30 μg/can and not larger than 100 μg/can-   Adsorption larger than 10 μg/can and not larger than 30 μg/can-   Adsorption not larger than 10 μg/can: (Superior)

The investigation results are given in Tables 13 and 14.

From Tables 9 to 14, the following facts are found for either can type.

Invention examples 1 to 3 and 5 are films in which modified polyolefinresin specified in the present invention is dispersed in polyester resinin which polyester type of mixed resin is change variously in a singlelayer, and invention examples 37 to 39 and 41 in which the films arelaminated under the laminating conditions of the present inventionexhibit very high formability, impact resistance, adhesion, and flavorproperty. Among these, invention example 39 in which the film ofinvention example 3 using adipic acid copolymerized polyethyleneterephthalate resin is laminated has a high performance as a whole, buthas a tendency toward deteriorated adhesion after heating and flavorproperty because of slightly low melting point of polyester resin andslightly low barrier property. Also, invention examples 68 and 72 inwhich invention examples 32 and 36 of films manufactured from acommercially available resin in which modified polyolefin resin isdispersed in polyester resin are laminated under the laminatingconditions of the present invention similarly exhibit high performance.On the other hand, comparative examples 1 to 5 are examples of films inwhich polyolefin resin is not contained in polyester resin in whichpolyester type is changed variously. Comparative examples 15 to 19 inwhich these films are laminated have especially low levels offormability and impact resistance.

Invention examples 4 to 8 are films using mixed resin in which variouspolyolefin resins of the present invention are dispersed in polyesterresin, and invention examples 40 to 44 in which these films arelaminated exhibit high formability, impact resistance, adhesion, andflavor property. However, invention example 44 in which the film ofinvention example 8 using polyolefin resin having a slightly highglass-transition temperature is laminated has a has a tendency-towardslightly deteriorated formability and impact resistance. On the otherhand, comparative examples 10 to 12 are mixed resins in which polyolefinresin containing a functional group derived from carboxylic acid whosepercentage deviates from the range of the present invention is dispersedin polyester resin, and comparative examples 24 to 26 in which thesemixed resins are laminated have inferior formability and impactresistance.

Invention examples 9 to 16 are films in which the blending ratio anddispersion state of modified polyolefin resin in polyester resin arechanged variously in the range of the present invention, and inventionexamples 45 to 52 in which the films are laminated under the laminatingconditions of the present invention exhibit high formability, impactresistance, adhesion, and flavor property. However, invention example 45in which the film of invention example 9 containing a small amount ofdispersed modified polyolefin resin is laminated and invention example51 in which the film of invention example 15 having a very large numberof grains of modified polyolefin resin is laminated have a tendencytoward slightly deteriorated impact resistance.

On the other hand, comparative examples 6 to 9 are films in which theblending ratio of modified polyolefin resin in polyester resin does notmeet the requirement of the present invention, and comparative examples20 to 23 in which the films are laminated under the laminatingconditions of the present invention have greatly deterioratedformability and impact resistance. Comparative example 20 in which thefilm of comparative example 6 containing a small amount of dispersedmodified polyolefin resin is laminated has greatly deterioratedroom-temperature impact resistance, and comparative example 23 in whichthe film of comparative example 9 containing a large amount of modifiedpolyolefin resin is laminated has greatly deteriorated formability.

Invention examples 27 to 31 are films in which titanium dioxide pigmentis mixed with a mixed resin of modified polyolefin resin and polyesterresin, and invention examples 63 to 67 in which the films are laminatedunder the laminating conditions of the present invention exhibit highformability, impact resistance, adhesion, and flavor property, and alsoprovide a white uniform color tone. However, invention example 63 inwhich the film of invention example 27 in which the added amount ofpigment is smaller than a desired range is laminated has slightlyinsufficient opacifying property of color tone. On the other hand,invention example 67 in which the film of invention example 31 in whichthe added amount of pigment is larger than a desired range is laminatedhas slightly deteriorated formability.

Invention examples 17 to 21 are films in which the blending ratio ofpolymerization catalyst and oxidation inhibitor in mixed resin ischanged variously in the range of the present invention, and inventionexamples 53 to 57 in which the films are laminated under the laminatingconditions of the present invention exhibit high formability, impactresistance, adhesion, and flavor property. However, invention example 53containing a large amount of oxidation inhibitor has slightlydeteriorated formability and impact resistance. On the other hand,comparative examples 27 and 28 in which the films of comparativeexamples 13 and 14 in which the blending ratio of polymerizationcatalyst and oxidation inhibitor in mixed resin deviates from the rangeof the present invention are laminated under the laminating conditionsof the present invention have deteriorated formability, impactresistance, and adhesion.

Invention examples 22 and 23 are films in which the thickness of eachlayer of film is changed, and invention examples 58 and 59 in which thefilms are laminated under the laminating conditions of the presentinvention exhibit high formability, impact resistance, adhesion, andflavor property. Since the film of invention example 22 is slightlythin, invention example 58 in which this film is laminated has slightlydeteriorated impact resistance.

Invention examples 41 and 73 to 76 are films obtained by changing thelaminating conditions for the film of invention example 5 in the rangeof the present invention. If the conditions are within the range of thepresent invention, high formability, impact resistance, adhesion, andflavor property are exhibited regardless of the laminating temperature.

Invention examples 24 and 25 are films in which a lubricant, freeradical inhibitor, and compatibilizing agent are mixed, respectively, ina mixed resin of modified polyolefin resin and polyester resin of thepresent invention, and invention examples 60 and 61 in which the filmsare laminated under the laminating conditions of the present inventionexhibit high formability, impact resistance, adhesion, and flavorproperty. Further, invention examples 60 and 61 also have lubricity,free radical deterioration resistance, and compatibility depending onthe function of added additive, and in particular, invention example 61containing a compatibilizing agent exhibits excellent low-temperatureimpact resistance.

Invention example 26 is a film of the present invention that ismanufactured by the two-axis stretching method, and invention examples62 and 77 in which the film is laminated exhibit high performance.Invention example 77, which has a plane orientation coefficient of0.015, exhibits a slightly deteriorated formability. Invention example62, which has a plane orientation coefficient in the range of thepresent invention, exhibits very high formability and impact resistance.

Invention examples 33 to 36 are two-layer films in which a polyesterresin layer containing no olefin is provided as an upper layer, andinvention examples 69 to 72 in which the two-layer films are laminatedhave high low-temperature impact resistance and flavor property ascompared with the single-layer film. However, invention example 71 inwhich the film of invention example 35 using a film containingpolybutylene terephthalate as an upper layer is laminated has a slightlydeteriorated flavor property.

TABLE 9 R1 layer Polyolefin resin Number of Weight Volume grains withpercentage Blend- percentage diameter of Polyester resin of functionaling of grains 0.1 to 5 μm *1) group derived ratio in with in cube withFilm Polymerization Oxidation from entire diameter one side of thick-Sample Resin catalyst (ppm) inhibitor Addi- Resin carboxylic Tg resin of0.1 to 10 μm ness film type (X) (ppm) (Y) X/Y tive type acid (wt %) (°C.) (wt %) 5 μm (vol %) (grains) (μm) Invention PET GeO₂ 100 ppm 400 ppm0.25 None EM4 8 <−30 15 12 2000 22 example 1 Invention PET/ GeO₂ 100 ppm400 ppm 0.25 None EM4 8 <−30 15 12 2000 22 example 2 PBT(60) InventionPET/ GeO₂ 100 ppm 400 ppm 0.25 None EM4 8 <−30 15 12 2000 22 example 3AD(20) Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EM2 18 <−30 1513 500 22 example 4 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 NoneEM4 8 <−30 15 12 2000 22 example 5 Invention PET/I(10) GeO₂ 100 ppm 400ppm 0.25 None EM5 7 <−30 15 12 2000 22 example 6 Invention PET/I(10)GeO₂ 100 ppm 400 ppm 0.25 None EM6 5 <−30 15 12 2000 22 example 7Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EM8 6     20 15 122000 22 example 8 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EM311 <−30 5 3 3 22 example 9 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25None EM3 11 <−30 5 5 70 22 example 10 Invention PET/I(10) GeO₂ 100 ppm400 ppm 0.25 None EM3 11 <−30 10 8 30 22 example 11 Invention PET/I(10)GeO₂ 100 ppm 400 ppm 0.25 None EM3 11 <−30 10 10 250 22 example 12Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EM3 11 <−30 15 15 50022 example 13 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EM3 11<−30 15 18 20000 22 example 14 Invention PET/I(10) GeO₂ 100 ppm 400 ppm0.25 None EM3 11 <−30 20 22 200000 22 example 15 Invention PET/I(10)GeO₂ 100 ppm 400 ppm 0.25 None EM3 11 <−30 28 20 8000 22 example 16Invention PET/I(10) GeO₂ 120 ppm 600 ppm 0.20 None EM6 5 <−30 15 12 200022 example 17 Invention PET/I(10) GeO₂ 100 ppm 100 ppm 1.0 None EM6 5<−30 15 12 2000 22 example 18 Invention PET/I(10) GeO₂ 100 ppm  10 ppm10 None EM6 5 <−30 15 12 2000 22 example 19 Invention PET/I(10) GeO₂ 50ppm  0.5 ppm  100 None EM6 5 <−30 15 12 2000 22 example 20 InventionPET/I(10) GeO₂ 50 ppm 0.05 ppm  1000 None EM6 5 <−30 15 12 2000 22example 21 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EM6 5 <−3015 12 2000 10 example 22 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25None EM6 5 <−30 15 12 2000 50 example 23 Invention PET/I(10) GeO₂ 100ppm 400 ppm 0.25 *3) EM3 11 <−30 15 12 2000 22 example 24 3 wt %Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 *4) EM3 11 <−30 15 12 200022 example 25 3 wt % Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 NoneEM4 8 <−30 15 12 2000 22 example 26 *1) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane is used as oxidationinhibitor. *3) Silicone of lubricant is added by 3 weight part to 100weight part of mixed resin. *4) Bond First 20B (manufactured by SumitomoChemical Co., Ltd.) of compatibilizing agent is added by 3 weight partto 100 weight part of mixed resin.

TABLE 10 Entire film R0 layer Film Polyester Film thickness Sample resinthickness (R1 + R0) Pigment film Resin type (μm) (μm) Type Content (wt%) *2) Stretching Invention example 1 22 None 0 Non-stretched Inventionexample 2 22 None 0 Non-stretched Invention example 3 22 None 0Non-stretched Invention example 4 22 None 0 Non-stretched Inventionexample 5 22 None 0 Non-stretched Invention example 6 22 None 0Non-stretched Invention example 7 22 None 0 Non-stretched Inventionexample 8 22 None 0 Non-stretched Invention example 9 22 None 0Non-stretched Invention example 10 22 None 0 Non-stretched Inventionexample 11 22 None 0 Non-stretched Invention example 12 22 None 0Non-stretched Invention example 13 22 None 0 Non-stretched Inventionexample 14 22 None 0 Non-stretched Invention example 15 22 None 0Non-stretched Invention example 16 22 None 0 Non-stretched Inventionexample 17 22 None 0 Non-stretched Invention example 18 22 None 0Non-stretched Invention example 19 22 None 0 Non-stretched Inventionexample 20 22 None 0 Non-stretched Invention example 21 22 None 0Non-stretched Invention example 22 10 None 0 Non-stretched Inventionexample 23 50 None 0 Non-stretched Invention example 24 22 None 0Non-stretched Invention example 25 22 None 0 Non-stretched Inventionexample 26 22 None 0 Two-axis stretched *2) Pigment content means weightpercentage (wt %) of pigment with respect to total film amount of entireresin and pigment.

TABLE 11 R1 layer Polyolefin resin Volume percent- Number of WeightBlend- age of grains with percentage ing grains diameter of functionalratio with di- of 0.1 group in ameter to 5 μm in Polyester resin derivedentire of cube with Film Polymerization *1) Oxida- from resin 0.1 to oneside of thick- Sample Resin catalyst (ppm) tion inhibitor Resincarboxylic Tg (wt 5 μm 10 μm ness film type (X) (ppm) (Y) X/Y Additivetype acid (wt %) (° C.) %) (vol %) (grains) (μm) Invention PET/I(10)GeO₂ 100 ppm 400 ppm 0.25 None EM5 7 <−30 15 12 2000 22 example 27Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EM5 7 <−30 15 12 200022 example 28 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EM5 7<−30 15 12 2000 22 example 29 Invention PET/I(10) GeO₂ 100 ppm 400 ppm0.25 None EM5 7 <−30 15 12 2000 22 example 30 Invention PET/I(10) GeO₂100 ppm 400 ppm 0.25 None EM5 7 <−30 15 12 2000 22 example 31 InventionPT4274 Sb₂O₃ 250 ppm 500 ppm 0.50 None EM5 10 <−30 15 12 2000 20 example32 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EM5 7 <−30 15 122000 20 example 33 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 NoneEM5 7 <−30 15 12 2000 20 example 34 Invention PET/I(10) GeO₂ 100 ppm 400ppm 0.25 None EM5 7 <−30 15 12 2000 20 example 35 Invention PT4274 Sb₂O₃250 ppm 500 ppm 0.50 None EM5 10 <−30 15 12 2000 20 example 36 InventionPET GeO₂ 100 ppm 400 ppm 0.25 None None — — 0 0 0 22 example 1Comparative PET/PBT(60) GeO₂ 100 ppm 400 ppm 0.25 None None — — 0 0 0 22example 2 Comparative PET/AD(20) GeO₂ 100 ppm 400 ppm 0.25 None None — —0 0 0 22 example 3 Comparative PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 NoneNone — — 0 0 0 22 example 4 Comparative PET/I(10) GeO₂ 100 ppm 400 ppm0.25 None None — — 0 0 0 22 example 5 Comparative PET/I(10) GeO₂ 100 ppm400 ppm 0.25 None EM3 11 <−30 2 2 3 22 example 6 Comparative PET/I(10)GeO₂ 100 ppm 400 ppm 0.25 None EM3 11 <−30 2 2 45 22 example 7Comparative PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EM3 11 <−30 35 2815000 22 example 8 Comparative PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 NoneEM3 11 <−30 35 28 120000 22 example 9 Comparative PET/I(10) GeO₂ 100 ppm400 ppm 0.25 None EM1 21 <−30 15 14 40 22 example 10 ComparativePET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EM7 1 <−30 15 3 20 22 example11 Comparative PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None EPR 0 <−30 15 15 22 example 12 Comparative PET/I(10) GeO₂ 40 ppm 400 ppm 0.10 None EM65 <−30 15 12 2000 22 example 13 Comparative PET/I(10) GeO₂ 40 ppm 400ppm 0.10 None EM6 5 <−30 15 12 2000 20 example 14 *1)Tetrakis-[methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane isused as oxidation inhibitor.

TABLE 12 Entire film R0 layer Film Polyester Film thickness PigmentSample resin thickness (R1 + R0) Content film Resin type (μm) (μm) Type(wt %) *2) Stretching Invention example 27 22 TiO₂ 3 Non-stretchedInvention example 28 22 TiO₂ 7 Non-stretched Invention example 29 22TiO₂ 15 Non-stretched Invention example 30 22 TiO₂ 30 Non-stretchedInvention example 31 22 TiO₂ 50 Non-stretched Invention example 32 20None 0 Non-stretched Invention example 33 PET 5 20 None 0 Non-stretchedInvention example 34 PET/I(10) 5 20 None 0 Non-stretched Inventionexample 35 PET/PBT(60) 5 20 None 0 Non-stretched Invention example 36PET 5 20 None 0 Non-stretched Comparative example 1 22 None 0Non-stretched Comparative example 2 22 None 0 Non-stretched Comparativeexample 3 22 None 0 Non-stretched Comparative example 4 22 None 0Non-stretched Comparative example 5 22 None 0 Two-axis stretchedComparative example 6 22 None 0 Non-stretched Comparative example 7 22None 0 Non-stretched Comparative example 8 22 None 0 Non-stretchedComparative example 9 22 None 0 Non-stretched Comparative example 10 22None 0 Non-stretched Comparative example 11 22 None 0 Non-stretchedComparative example 12 22 None 0 Non-stretched Comparative example 13 22None 0 Non-stretched Comparative example 14 PET 5 20 None 0Non-stretched *2) Pigment content means weight percentage (wt %) ofpigment with respect to total film amount of entire resin and pigment.

TABLE 13 Melting point of R1 layer Thin-wall deep drawn can Drawn andironed can (DI can) Laminated polyester Laminating Plane Impact ImpactAdhesion Adhesion Impact Impact Adhesion Adhesion metal Sample resintemp. orientation Forma- resistance resistance after after Flavorresistance resistance after after Flavor sheet film (° C.) (° C.)coefficient bility (room temp.) (low temp.) forming heating propertyFormability (room temp.) (low temp.) forming heating property InventionInvention 255 240 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 37 example 1Invention Invention 235 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ exampleexample 38 2 Invention Invention 220 210 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example example 39 3 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 40 4 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 41 5 Invention Invention 230 2150 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 42 6 InventionInvention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 43 7Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 44example 8 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example example 45 9 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 46 example 10 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 47 11 Invention Invention 230215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 48 12 InventionInvention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 49 example13 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ exampleexample 50 14 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example example 51 15 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 52 example 16 Invention Invention 230 215 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 53 example 17 Invention Invention230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 54 18Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 55example 19 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 56 example 20 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 57 21 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 58 example 22 Invention Invention 230215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 59 example 23 InventionInvention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 6024 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example61 example 25 Invention Invention 230 215 0.005 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ example 62 example 26

TABLE 14 Melting point of R1 layer Thin-wall deep drawn can Drawn andironed can (DI can) Laminated polyester Laminating Plane Impact ImpactAdhesion Adhesion Impact Impact Adhesion Adhesion metal Sample resintemp. orientation Forma- resistance resistance after after Flavorresistance resistance after after Flavor sheet film (° C.) (° C.)coefficient bility (room temp.) (low temp.) forming heating propertyFormability (room temp.) (low temp.) forming heating property InventionInvention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 63 example27 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example64 example 28 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 65 example 29 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 66 30 Invention Invention 230 215 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 67 example 31 Invention Invention255 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 68 example 32Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ exampleexample 69 33 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 70 example 34 Invention Invention 230 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 71 example 35 Invention Invention 255 215 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 72 36 Invention Invention230 260 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 73 example 5 InventionInvention 230 230 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 74 example 5Invention Invention 230 190 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 75example 5 Invention Invention 230 170 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 76 example 5 Invention Invention 230 200 0.015 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 77 26 Comparative Comparative 215 200 0 ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 15 example 1 ComparativeComparative 220 210 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 16 example2 Comparative Comparative 230 210 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 17 example 3 Comparative Comparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 18 4 Comparative Comparative 240 220 0.015⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 19 example 5 ComparativeComparative 245 225 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 20 example6 Comparative Comparative 255 235 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 21 example 7 Comparative Comparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 22 8 Comparative Comparative 235 215 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 23 example 9 Comparative Comparative235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 24 example 10Comparative Comparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 25 example 11 Comparative Comparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 26 12 Comparative Comparative 235 215 0⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 27 example 13 ComparativeComparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 28 example14

Example 4

As a resin raw material, modified polyolefin resin with group derivedfrom carboxylic acid was cold blended with polyester resin in a blendingratio given in Tables 15 and 16 by using a tumbler blender, and then theblended resin was melted and kneaded at 270° C. by using a two-axisextruding machine, by which a raw material pellet of polyester resin inwhich modified polyolefin resin was dispersed was obtained. Partially, acommercially available resin (Sealer PT4274 manufactured byMitsui-DuPont Polychemical Co., Ltd.) that had been pelletized inadvance in a state in which modified polyolefin resin with group derivedfrom carboxylic acid was dispersed in polyester resin, which was used asa resin raw material, was used as it was. In the tables, the resin typecorresponding to the symbol of resin type of polyester resin and resintype of polyolefin resin is the same as that described in Example 3.

As a metal sheet, as in Example 3, a tin-free steel (hereinafterabbreviated to TFS) with a thickness of 0.18 mm for thin-wall deep drawncan and 0.23 mm for DI can, which had a degree of temper of DR9,metallic chromium layer of 80 mg/m², and chromium oxide layer of 15mg/m² (metallic chromium conversion), was used, by which a both-sideresin laminated metal-sheet was obtained by a method in which the rawmaterial resin pellet was inserted in a one-axis extruding machine, aresin for R0 layer was inserted in a separate extruding machine in thecase of two layers and simultaneously melted and extruded, molten resinwas extruded directly onto one surface of the metal sheet, the extrudedresin was once cooled while being held adherently between two rolls, andimmediately after the resin was laminated on the opposite surface in thesame manner, the resin laminated metal sheet was cooled rapidly inwater. The temperature of metal sheet at the laminating time was 230° C.The lip opening width of T die was adjusted so that the thickness ofresin film was 10 to 50 μm. The type of sample resin and the resinmelting temperature at the laminating time are given in Tables 15 to 18.The used polyester resin and modified polyolefin resin with groupderived from carboxylic acid are the same as those used in Example 3.

All of the grain diameter of modified polyolefin resin dispersed inresin film, various temperatures in the table, and the method formeasuring the plane orientation coefficient of resin laminated metalsheet are the same as those in Example 3. As in Example 3, a thin-walldeep drawn can or a DI can was manufactured from the resin laminatedmetal sheet obtained as described above, and the can was subjected tostraightening heat treatment to manufacture a sample can. Theformability, impact resistance, adhesion, and flavor property of film ofthe manufactured can body were investigated as in Example 3.

The investigation results are given in Tables 17 and 18.

From Tables 15 to 18, the following facts are found for either can type.

Invention examples 78 to 80 and 81 are resin layers formed in a singlelayer, in which modified polyolefin resin specified in the presentinvention is dispersed in polyester resin in which polyester type ofmixed resin is changed variously, and exhibit high formability, impactresistance, adhesion, and flavor property. Among these, inventionexample 80 using adipic acid copolymerized polyethylene terephthalateresin has high performance as a whole, but has a tendency towarddeteriorated adhesion after heating and flavor property because ofslightly low melting point of polyester resin and slightly low barrierproperty. Also, invention examples 108 and 112 manufactured from acommercially available resin in which modified polyolefin resin isdispersed in polyester resin similarly exhibit high performance. On theother hand, comparative examples 29 to 32 are examples of resins inwhich polyolefin resin is not contained in polyester resin in whichpolyester type is changed variously. These resins especially have lowlevels of formability and impact resistance.

Invention examples 81 to 85 use mixed resin in which various polyolefinresins of the present invention are dispersed in polyester resin, andexhibit high formability, impact resistance, adhesion, and flavorproperty. However, invention example 85 using polyolefin resin having aslightly high glass-transition temperature has a tendency towardslightly deteriorated formability and impact resistance. On the otherhand, comparative examples 37 to 39 are mixed resins in which polyolefinresin containing a functional group derived from carboxylic acid whosepercentage deviates from the range of the present invention is dispersedin polyester resin, and have inferior formability and impact resistance.

Invention examples 86 to 93 are resin layers obtained by laminating,under the laminating conditions of the present invention, mixed resinsin which the blending ratio and dispersion state of modified polyolefinresin in polyester resin are changed variously in the range of thepresent invention, and exhibit high formability, impact resistance,adhesion, and flavor property. However, invention example 86 containinga small amount of dispersed modified polyolefin resin and inventionexample 92 (93) having a very large number of grains of modifiedpolyolefin resin have a tendency toward slightly deteriorated impactresistance.

On the other hand, comparative examples 33 to 36 are resin layers inwhich the blending ratio of modified polyolefin resin in polyester resindoes not meet the requirement of the present invention, and have greatlydeteriorated formability and impact resistance. Comparative example 33containing a small amount of dispersed modified polyolefin resin hasgreatly deteriorated room-temperature impact resistance, and comparativeexample 36 containing a large amount of modified polyolefin resin hasgreatly deteriorated formability. Comparative examples 35 and 36containing a large amount of modified polyolefin resin also have aproblem with flavor.

Invention examples 103 to 107 are mixed resin layers in which titaniumdioxide pigment is mixed with a mixed resin of modified polyolefin resinand polyester resin, and exhibit high formability, impact resistance,adhesion, and flavor property, and also provide a white uniform colortone. However, invention example 103 in which the added amount ofpigment is smaller than a desired range has slightly insufficientopacifying property of color tone. On the other hand, invention example107 in which the added amount of pigment is larger than a desired rangehas slightly deteriorated formability.

Invention examples 94 to 98 are resin layers in which the blending ratioof polymerization catalyst and oxidation inhibitor in mixed resin ischanged variously in the range of the present invention, and exhibithigh formability, impact resistance, adhesion, and flavor property.However, invention example 94 containing a large amount of oxidationinhibitor has slightly deteriorated formability and impact resistance.On the other hand, comparative examples 40 and 41 in which the blendingratio of polymerization catalyst and oxidation inhibitor in mixed resindeviates from the range of the present invention have deterioratedformability, impact resistance, and adhesion.

Invention examples 99 and 100 are resin layers in which the thickness ofeach layer is changed, and exhibit high formability, impact resistance,adhesion, and flavor property. Since the resin layer of inventionexample 99 is slightly thin, the impact resistance is slightlydeteriorated.

Invention examples 101 and 102 are resin layers in which a lubricant,free radical inhibitor, and compatibilizing agent are mixed,respectively, in a mixed resin of modified polyolefin resin andpolyester resin of the present invention, and exhibit high formability,impact resistance, adhesion, and flavor property. Further, inventionexamples 101 and 102 also have lubricity, free radical deteriorationresistance, and compatibility depending on the function of addedadditive, and in particular, invention example 102 containing acompatibilizing agent exhibits excellent low-temperature impactresistance.

Invention examples 109 to 112 are two-layer resins in which a polyesterresin layer containing no olefin is provided as an upper layer, and havehigh low-temperature impact resistance and flavor property as comparedwith the single-layer resin. However, invention example 111 using aresin containing polybutylene terephthalate as an upper layer has aslightly deteriorated flavor property.

TABLE 15 R1 layer Polyester resin Number of grains with Weight diameterof percentage Blending Volume 0.1 to 5 μm Polyester resin of functionalratio in percentage of in cube with Polymerization Polyester groupderived entire grains with one side of Sample Resin catalyst (ppm) *1)Oxidation meloting point Polyolefin from carboxylic Tg resin diameter of0.1 10 μm Film thickness film type (X) inhibitor (ppm) (Y) X/Y Additive(° C.) resin acid (wt %) (° C.) (wt %) to 5 μm (vol %) (grains) (μm)Invention PET GeO₂ 100 ppm 400 ppm 0.25 None 255 EM4 8 <−30 15 14 250025 example 78 Invention PET/PBT(60) GeO₂ 100 ppm 400 ppm 0.25 None 235EM4 8 <−30 15 14 2500 25 example 79 Invention PET/AD(20) GeO₂ 100 ppm400 ppm 0.25 None 220 EM4 8 <−30 15 14 2500 25 example 80 InventionPET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM2 18 <−30 15 14 1000 25example 81 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM4 8<−30 15 14 2500 25 example 82 Invention PET/I(10) GeO₂ 100 ppm 400 ppm0.25 None 230 EM5 7 <−30 15 14 2500 25 example 83 Invention PET/I(10)GeO₂ 100 ppm 400 ppm 0.25 None 230 EM6 5 <−30 15 14 2500 25 example 84Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM8 6 20 15 142500 25 example 85 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None230 EM3 11 <−30 5 4 4 25 example 86 Invention PET/I(10) GeO₂ 100 ppm 400ppm 0.25 None 230 EM3 11 <−30 5 8 100 25 example 87 Invention PET/I(10)GeO₂ 100 ppm 400 ppm 0.25 None 230 EM3 11 <−30 10 10 50 25 example 88Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM3 11 <−30 10 12500 25 example 89 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230EM3 11 <−30 15 18 800 25 example 90 Invention PET/I(10) GeO₂ 100 ppm 400ppm 0.25 None 230 EM3 11 <−30 15 20 22000 25 example 91 InventionPET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM3 11 <−30 20 24 250000 25example 92 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM3 11<−30 28 22 10000 25 example 93 Invention PET/I(10) GeO₂ 120 ppm 600 ppm0.2 None 230 EM6 5 <−30 15 14 2500 25 example 94 Invention PET/I(10)GeO₂ 100 ppm 100 ppm 1 None 230 EM6 5 <−30 15 14 2500 25 example 95Invention PET/I(10) GeO₂ 100 ppm  10 ppm 10 None 230 EM6 5 <−30 15 142500 25 example 96 Invention PET/I(10) GeO₂ 50 ppm  0.5 ppm  100 None230 EM6 5 <−30 15 14 2500 25 example 97 Invention PET/I(10) GeO₂ 100 ppm0.05 ppm  1000 None 230 EM6 5 <−30 15 14 2500 25 example 98 InventionPET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM6 5 <−30 15 14 2500 10example 99 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM6 5<−30 15 14 2500 50 example 100 Invention PET/I(10) GeO₂ 100 ppm 400 ppm0.25 *3) 3 230 EM3 11 <−30 15 14 2500 25 example 101 wt % InventionPET/I(10) GeO₂ 100 ppm 400 ppm 0.25 *4) 3 230 EM3 11 <−30 15 14 2500 25example 102 wt % *1) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane is used as oxidationinhibitor. *3) Silicone of lubricant is added by 3 weight part to 100weight part of mixed resin. *4) Bond First 20B (manufactured by SumitomoChemical Co., Ltd.) of compatibilizing agent is added by 3 weight partto 100 weight part of mixed resin. Table 15

TABLE 16 R1 layer Polyester resin Number of Weight grains withpercentage Blending Volume diameter of Polyester resin of functionalratio in percentage of 0.1 to 5 μm Polymerization *1) Oxida- Polyestermeloting group derived entire grains with in cube with Film Sample Resincatalyst (ppm) tion inhibitor point from carboxylic Tg resin diameter of0.1 one side of thickness film type (X) (ppm) (Y) X/Y Additive (° C.)Polyolefin resin acid (wt %) (° C.) (wt %) to 5 μm (vol %) 10 μm(grains) (μm) Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM57 <−30 15 14 2500 25 example 103 Invention PET/I(10) GeO₂ 100 ppm 400ppm 0.25 None 230 EM5 7 <−30 15 14 2500 25 example 104 InventionPET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM5 7 <−30 15 14 2500 25example 105 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM5 7<−30 15 14 2500 25 example 106 Invention PET/I(10) GeO₂ 100 ppm 400 ppm0.25 None 230 EM5 7 <−30 15 14 2500 25 example 107 Invention PT4274Sb₂O₃ 250 ppm 500 ppm 0.5 None 255 EM5 10 <−30 15 14 2500 22 example 108Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM5 7 <−30 15 142500 20 example 109 Invention PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None230 EM5 7 20 15 14 2500 20 example 110 Invention PET/I(10) GeO₂ 100 ppm400 ppm 0.25 None 230 EM5 7 <−30 15 14 2500 20 example 111 InventionPT4274 Sb₂O₃ 250 ppm 500 ppm 0.5 None 255 EM5 10 <−30 15 14 2500 20example 112 Comparative PET GeO₂ 100 ppm 400 ppm 0.25 None 255 None — —0 0 0 25 example 29 Comparative PET/PBT(60) GeO₂ 100 ppm 400 ppm 0.25None 235 None — — 0 0 0 25 example 30 Comparative PET/AD(20) GeO₂ 100ppm 400 ppm 0.25 None 220 None — — 0 0 0 25 example 31 ComparativePET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 None — — 0 0 0 25 example32 Comparative PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM3 11 <−302 3 5 25 example 33 Comparative PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None230 EM3 11 <−30 2 3 50 25 example 34 Comparative PET/I(10) GeO₂ 120 ppm400 ppm 0.25 None 230 EM3 11 <−30 35 30 20000 25 example 35 ComparativePET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM3 11 <−30 35 30 135000 25example 36 Comparative PET/I(10) GeO₂ 100 ppm 400 ppm 0.25 None 230 EM121 <−30 15 16 50 25 example 37 Comparative PET/I(10) GeO₂ 100 ppm 400ppm 0.25 None 230 EM7 1 <−30 15 4 40 25 example 38 Comparative PET/I(10)GeO₂ 100 ppm 400 ppm 0.25 None 230 EPR 0 <−30 15 1 4 25 example 39Comparative PET/I(10) GeO₂ 40 ppm 400 ppm 0.1 None 230 EM6 5 <−30 15 142500 25 example 40 Comparative PET/I(10) GeO₂ 40 ppm 400 ppm 0.1 None230 EM6 5 <−30 15 14 2500 20 example 41 *1) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane is used as oxidationinhibitor.

TABLE 17 Melting temp. of Investigation result R0 layer Entire film R1layer Thin-wall deep drawn can Drawn and ironed can (DI can) PolyesterFilm resin at Impact Impact Impact Impact resin Film thickness Pigmentextrusion resistance resistance Adhesion Adhesion resistance resistanceAdhesion Adhesion Sample Resin thickness (R1 + R0) Content laminatingForma- (room (low after after Flavor Forma- (room (low after afterFlavor film type (μm) (μm) Type (wt %) *2) time (° C.) bility temp.)temp.) forming heating property bility temp.) temp.) forming heatingproperty Invention 25 None 0 285 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example78 Invention 25 None 0 265 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 79Invention 25 None 0 250 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 80Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 81Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 82Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 83Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 84Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 85Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 86Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 87Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 88Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 89Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 90Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 91Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 92Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 93Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 94Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 95Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 96Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 97Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 98Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 99Invention 10 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 100Invention 50 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 101Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 101Invention 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 102 *2)Pigment content means weight percentage (wt %) of pigment with respectto total film amount of entire resin and pigment. Pigment is added to R1layer.

TABLE 18 Melting temp. of Investigation result R0 layer Entire film R1layer Thin-wall deep drawn can Drawn and ironed can (DI can) PolyesterFilm resin at Impact Impact Impact Impact resin Film thickness Pigmentextrusion resistance resistance Adhesion Adhesion resistance resistanceAdhesion Adhesion Sample Resin thickness (R1 + R0) Content laminatingForma- (room (low after after Flavor Forma- (room (low after afterFlavor film type (μm) (μm) Type (wt %) *2) time (° C.) bility temp.)temp.) forming heating property bility temp.) temp.) forming heatingproperty Invention 25 TiO₂ 3 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example103 Invention 25 TiO₂ 7 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 104Invention 25 TiO₂ 15 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 105Invention 25 TiO₂ 30 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 106Invention 25 TiO₂ 50 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 107Invention 25 None 0 285 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 108Invention PET 5 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example109 Invention PET/I 5 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 110 (10) Invention PET/PBT 5 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example (60) 111 Invention PET 5 25 None 0 285 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 112 Comparative 25 None 0 285 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 29 Comparative 25 None 0 265 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 30 Comparative 25 None 0 250 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ example 31 Comparative 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ example 32 Comparative 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 33 Comparative 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 34 Comparative 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 35 Comparative 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 36 Comparative 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 37 Comparative 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 38 Comparative 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 39 Comparative 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 40 Comparative 25 None 0 260 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 41 *2) Pigment content means weight percentage (wt %) of pigmentwith respect to total film amount of entire resin and pigment. Pigmentis added to R1 layer.

Example 5

As a resin raw material for R1 layer, modified polyolefin resin withgroup derived from carboxylic acid having a primary grain diameter of0.3 μm was cold blended with polyester resin in a blending ratio givenin Tables 19 and 20 by using a tumbler blender, and then the blendedresin was melted and kneaded at 270° C. by using a two-axis extrudingmachine, by which a raw material pellet of polyester resin in whichmodified polyolefin resin was dispersed was obtained. On the other hand,polyester resin containing no modified polyolefin resin, which was aresin raw material for R0 layer, was inserted in a separate one-axisextruding machine, and each of molten resins was introduced into amulti-manifold type T die and extruded in two layers while the filmthickness of R1 and R0 layers was controlled by the discharge amount ofmolten resin from the extruding machine, by which a resin film with atotal thickness of 9.5 to 70 μm was manufactured continuously whilebeing cooled by the surface of a rotating metallic roll.

The used polyester resin and modified polyolefin resin with groupderived from carboxylic acid were as follows:

1. Polyester Resin

(1) PET/PBT(90): Mixed resin with a ratio of polyethylene terephthalate(EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutyleneterephthalate (Planac manufactured by Dainippon Ink & chemicals, Inc.)of 10:90, intrinsic viscosity: 0.6 dl/g, Tg: 27° C., Tc: 60° C., Tm:215° C., Ge content: 10 ppm

(2) PET/PBT(80): Mixed resin with a ratio of polyethylene terephthalate(EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutyleneterephthalate (Planac manufactured by Dainippon Ink & chemicals, Inc.)of 20:80, intrinsic viscosity: 0.6 dl/g, Tg: 35° C., Tc: 75° C., Tm:220° C., Ge content: 10 ppm

(3) PET/PBT(70): Mixed resin with a ratio of polyethylene terephthalate(EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutyleneterephthalate (Planac manufactured by Dainippon Ink & chemicals, Inc.)of 30:70, intrinsic viscosity: 0.62 dl/g, Tg: 45° C., Tc: 90° C., Tm:230° C., Ge content: 20 ppm

(4) PET/PBT(60): Mixed resin with a ratio of polyethylene terephthalate(EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutyleneterephthalate (Planac manufactured by Dainippon Ink & chemicals, Inc.)of 40:60, intrinsic viscosity: 0.6 dl/g, Tg: 50° C., Tc: 105° C., Tm:235° C. Ge content-10 ppm

(5) PET/PBT(40): Mixed resin with a ratio of polyethylene terephthalate(EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutyleneterephthalate(Planac manufactured by Dainippon Ink & chemicals, Inc.) of 60:40,intrinsic viscosity: 0.6 dl/g, Tg: 60° C., Tc: 120° C., Tm: 240° C., Gecontent: 10 ppm

(6) PET/PBT(20): Mixed resin with a ratio of polyethylene terephthalate(EFG10 manufactured by Kanebo Gohsen, Ltd.) to polybutyleneterephthalate (Planac manufactured by Dainippon Ink & chemicals, Inc.)of 80:20, intrinsic viscosity: 0.6 dl/g, Tg: 65° C., Tc: 140° C., Tm:245° C., Ge content: 10 ppm

(7) PET: Polyethylene terephthalate (EFG10 manufactured by KaneboGohsen, Ltd.), intrinsic viscosity: 0.62 dl/g, Tg: 72° C., Tc: 150° C.,Tm: 255° C., Ge content: 20 ppm

(8) PET/I (10): Ethylenephthalate-ethyleneisophthalate copolymerizedresin with a ratio of terephthalic acid to isophthalic acid of 90:10(IP121B manufactured by Kanebo Gohsen, Ltd.), intrinsic viscosity: 0.6dl/g, Tg: 70° C., Tc: 170° C., Tm: 230° C., Ge content: 10 ppm

2. Modified Polyolefin Resin with Group Derived from Carboxylic Acid

(1) EM1: Polymethyl methacrylate-(ethylene-ethyl acrylate copolymer)graft copolymer (Modiper A5200 manufactured by NOF Corp.), weight ratioof functional group derived from carboxylic acid: 21 wt %,glass-transition temperature: −30° C. or lower

(2) EM2: Polymethyl methacrylate-(ethylene-ethyl acrylate-maleicanhydride copolymer) graft copolymer (Modiper A8200 manufactured by NOFCorp.), weight ratio of functional group derived from carboxylic acid:18 wt %, glass-transition temperature: −30° C. or lower

(3) EM3: Ethylene-ethyl acrylate-maleic anhydride copolymer (BondineHX8290 manufactured by Sumitomo Chemical Co., Ltd.), weight ratio offunctional group derived from carboxylic acid: 11 wt %, glass-transitiontemperature: −30° C. or lower

(4) EM4: Ethylene-methacrylic acid copolymer (Nucrel N1560 manufacturedby Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functionalgroup derived from carboxylic acid: 8 wt %, glass-transitiontemperature: −30° C. or lower

(5) EM5: 50% Zn neutralized substance of ethylene-methacrylic acidcopolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical Co.,Ltd. neutralized partially by Zn), weight ratio of functional groupderived from carboxylic acid: 7 wt %, glass-transition temperature: −30°C. or lower

(6) EM6: 60% Zn neutralized substance of ethylene-methacrylic acidcopolymer (Himilan 1557 manufactured by Mitsui-DuPont Polychemical Co.,Ltd.), weight ratio of functional group derived from carboxylic acid: 5wt %, glass-transition temperature: −30° C. or lower

(7) EM7: Ethylene-methacrylic acid copolymer (Nucrel N0200H manufacturedby Mitsui-DuPont Polychemical Co., Ltd.), weight ratio of functionalgroup derived from carboxylic acid: 1 wt %, glass-transitiontemperature: −30° C. or lower

(8) EM8: Polystyrene-(ethylene-ethyl acrylate copolymer) graft copolymer(Modiper A5100 manufactured by NOF Corp.), weight ratio of functionalgroup derived from carboxylic acid: 6 wt %, glass-transitiontemperature: 20° C.

(9) EPR: Ethylene-propylene rubber (EP07P manufactured by JSR Corp.),weight ratio of functional group derived from carboxylic acid: 0 wt %,glass-transition temperature: −30° C. or lower

As a resin raw material for R1 layer, pelletized modified polyolefinresin with group derived form carboxylic acid and polyester resin areinserted in a one-axis extruding machine in the blending ratio shown incomparative example 16 in Table 20. On the other hand, polyester resincontaining no modified polyolefin resin, which was a resin raw materialfor R0 layer, was inserted in a separate one-axis extruding machine, andeach of molten resins was introduced into a multi-manifold type T dieand extruded in two layers while the film thickness of R1 and R0 layerswas controlled by the discharge amount of molten resin from theextruding machine, by which a resin film with a total thickness of 9.5to 70 μm was manufactured continuously while being cooled by the surfaceof a rotating metallic roll.

A resin laminated metal sheet was obtained by a thermo-compressionbonding method in which the resin film obtained as described above washot-pressed on both surfaces of a tin-free steel (hereinafterabbreviated to TFS, thickness: 0.18 mm for thin-wall deep drawn can and0.23 mm for DI can, degree of temper: DR9, metallic chromium layer: 80mg/m², chromium oxide layer: 15 mg/m² (metallic chromium conversion))heated by an induction heating system, and then the laminated metalsheet was rapidly cooled in water. The metal sheet temperature at thelaminating time (laminating temperature) is given in Tables 21 and 22.

The grain diameter of modified polyolefin resin dispersed in R1 layer ofresin film, various temperatures in the table, and the plane orientationcoefficient of resin laminated metal sheet were measured by the samemethod as that in Example 1.

A thin-wall deep drawn can or a DI can was manufactured from thelaminated metal sheet obtained as described above, and the can wassubjected to straightening heat treatment to manufacture a sample can.The formability, impact resistance (room temperature, low temperature),adhesion after forming, adhesion after heating, and retort resistance offilm of the manufactured can body were investigated. The retortresistance was evaluated by cloudiness of film at the can bottom afterretorting (cloudiness resistance). The lid was obtained by forming theresin laminated metal sheet in the same way as a can lid of acommercially available 250 ml negative-pressure can (three-piece can).

The following is a detailed description of the investigation method.

1. Evaluation by Thickness-decreasing Deep Drawing

1-1 Can Manufacturing

A resin laminated metal sheet was subjected to first-stage drawing andredrawing under the following conditions, by which a thin-wall deepdrawn can was obtained.

-   First-stage drawing    -   Blank diameter . . . 150 to 160 mm    -   First-stage drawing . . . drawing ratio: 1.65-   Redrawing    -   Primary redrawing . . . drawing ratio: 1.25    -   Secondary redrawing . . . drawing ratio: 1.25    -   Radius of curvature of die corner in redrawing process . . . 0.4        mm    -   Load for pressing wrinkle at the time of redrawing . . . 39227N        (4000 kg)-   Average thickness decreasing percentage of can sidewall    -   40 to 55% with respect to thickness of resin laminated metal        sheet before forming        1-2 Straightening Heat Treatment

Forming strain of film caused by can manufacturing was removed bykeeping the can in a thermal environment of film melting point minus 15°C. for 30 seconds and then by rapidly cooling it.

Formability

Evaluation was made as described below by the limit of capability formanufacturing can without film failure. Grades not lower than ◯ markedgrade are acceptable.

Limit of forming (thickness decreasing percentage): Grade

-   Incapable of forming at thickness decreasing percentage of 40%:    (Inferior)-   Capable of forming up to thickness decreasing percentage of 40%-   Capable of forming up to thickness decreasing percentage of 45%-   Capable of forming up to thickness decreasing percentage of 50%-   Capable of forming up to thickness decreasing percentage of 55%:    (Superior)    (2) Evaluation of Room-temperature and Low-temperature Impact    Resistance

A can body (thickness decreasing percentage: 50%) subjected tostraightening heat treatment was necked, and the can body was filledwith distilled water. After a lid was installed and tightened, an ironball of 0.5 kg was dropped from a height of 30 cm to give a shock to thecan bottom. Thereafter, the lid was opened, and 1% salt water was pouredin the can so that a portion that had suffered shock was immersed. Afterimmersion for five minutes, a load of 6 V was applied across a platinumelectrode immersed in the liquid and a can metal portion, and thecurrent value after five minutes was read, by which evaluation was madeas described below. The same tests were conducted at room temperature of20° C. and at a temperature of 0° C. The former test was for evaluatingroom-temperature impact resistance, and the latter test was forevaluating low-temperature impact resistance. Grades not lower than ◯marked grade are acceptable.

(Evaluation of Room-temperature Impact Resistance)

Test Result: Grade

-   Current value not lower than 30 mA: (Inferior)-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA-   Current value not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA: (Superior)    (Evaluation of Low-temperature Impact Resistance)    Test Result: Grade-   Current value not lower than 50 mA: (Inferior)-   Current value not lower than 30 mA and lower than 50 mA-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA-   Current value not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA: (Superior)    (3) Adhesion After Forming

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was immersed in aqueous solutioncontaining 1.5 wt % citric acid and 1.5 wt % sodium chloride for 24hours. Thereafter, the peeling length of resin in the can end portionwas observed, and evaluation was made as described below. Grades notlower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling length longer than 10 mm (Inferior)-   Peeling length longer than 5 mm and not longer than 10 mm-   Peeling length longer than 2 mm and not longer than 5 mm-   Peeling length not longer than 2 mm,-   No peeling: (Superior)    (4) Adhesion After Heating

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was heated without content therein at210° C. for 10 minutes in an oven. Thereafter, the degree of peeling ofresin in the can end portion was observed, and evaluation was made asdescribed below. Grades not lower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling percentage higher than 10%: (Inferior)-   Peeling percentage higher than 5% and not higher than 10%-   Peeling percentage higher than 2% and not higher than 5%-   Peeling percentage higher than 0.5% and not higher than 2%-   Peeling percentage not higher than 0.5%-   No peeling: (Superior)    (5) Cloudiness of Film After Retorting

A can body (thickness decreasing percentage: 50%) subjected tostraightening heat treatment was necked, and the can body was filledwith distilled water. After a lid was installed and tightened, the canwas cooled to 4° C., and thereafter retorting was performed in anatmosphere of 130° C. for one hour. After retorting, the degree ofcloudiness of film at the can bottom was observed. Grades not lower than◯ marked grade are acceptable.

Test Result: Grade

-   Cloudiness more than 50% of the whole: (Inferior)-   Cloudiness more than 10% of the whole and not more than 50%-   Cloudiness more than 2% of the whole and not more than 10%-   Very slight cloudiness (not more than 2% of the whole)-   No change: (Superior)    2. Evaluation by Drawing and Ironing (DI Forming)    2-1 Can Manufacturing

A resin laminated metal sheet was drawn and ironed under the followingconditions, by which a DI can was obtained.

-   First-stage drawing    -   Blank diameter: 150 mm    -   Drawing ratio: 1.6-   Second-stage drawing    -   Drawing ratio: 1.25-   Ironing    -   Ironing punch diameter: 3-stage ironing 65.8 mm dia-   Total ironing percentage of can sidewall    -   55 to 70% with respect to thickness of resin laminated metal        sheet before forming        1-2 Straightening Heat Treatment

Forming strain of film caused by can manufacturing was removed bykeeping the can in a thermal environment of film melting point minus 15°C. for 30 seconds and then by rapidly cooling it.

(1) Formability

Evaluation was made as described below by the limit of capability formanufacturing can without film failure. Grades not lower than ◯ markedgrade are acceptable.

Limit of forming (total ironing percentage): Grade

-   Incapable of forming at total ironing percentage of 55%: (Inferior)-   Capable of forming up to total ironing percentage of 55%-   Capable of forming up to total ironing percentage of 60%-   Capable of forming up to total ironing percentage of 65%-   Capable of forming up to total ironing percentage of 70%: (Superior)    (2) Evaluation of Room-temperature and Low-temperature Impact    Resistance

A can body (total ironing percentage: 65%) subjected to straighteningheat treatment was necked, and the can body was filled with distilledwater. After a lid was installed and tightened, an iron ball of 0.5 kgwas dropped from a height of 25 cm to give a shock to the can bottom.Thereafter, the lid was opened, and 1% salt water was poured in the canso that a portion that had suffered shock was immersed. After immersionfor five minutes, a load of 6 V was applied across a platinum electrodeimmersed in the liquid and a can metal portion, and the current valueafter five minutes was read, by which evaluation was made as describedbelow. The same tests were conducted at room temperature of 20° C. andat a temperature of 0° C. The former test was for evaluatingroom-temperature impact resistance, and the latter test was forevaluating low-temperature impact resistance. Grades not lower than ◯marked grade are acceptable.

(Evaluation of Room-temperature Impact Resistance)

Test Result: Grade

-   Current value not lower than 30 mA: (Inferior)-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA-   Current value not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA: (Superior)    (Evaluation of Low-temperature Impact Resistance)    Test Result: Grade-   Current value not lower than 50 mA: (Inferior)-   Current value not lower than 30 mA and lower than 50 mA-   Current value not lower than 10 mA and lower than 30 mA-   Current value not lower than 5 mA and lower than 10 mA-   Current value not lower than 1 mA and lower than 5 mA-   Current value lower than 1 mA: (Superior)    (3) Adhesion After Forming

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was immersed in aqueous solutioncontaining 1.5 wt % citric acid and 1.5 wt % sodium chloride for fivehours. Thereafter, the peeling length of resin in the can end portionwas observed, and evaluation was made as described below. Grades notlower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling length longer than 10 mm: (Inferior)-   Peeling length longer than 5 mm and not longer than 10 mm-   Peeling length longer than 2 mm and not longer than 5 mm-   Peeling length not longer than 2 mm-   No peeling: (Superior)    (4) Adhesion After Heating

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was heated without content therein at210° C. for 10 minutes in an oven. Thereafter, the degree of peeling ofresin in the can end portion was observed, and evaluation was made asdescribed below. Grades not lower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling percentage higher than 10%: (Inferior)-   Peeling percentage higher than 5% and not higher than 10%-   Peeling percentage higher than 2% and not higher than 5%-   Peeling percentage higher than 0.5% and not higher than 2%-   Peeling percentage not higher than 0.5%-   No peeling: (Superior)    (5) Cloudiness of Film After Retorting (Cloudiness Resistance)

A can body (total ironing percentage: 65%) subjected to straighteningheat treatment was necked, and the can body was filled with distilledwater. After a lid was installed and tightened, the can was cooled to 4°C., and thereafter retorting was performed in an atmosphere of 130° C.for one hour. After retorting, the degree of cloudiness of film at thecan bottom was observed. Grades not lower than ◯ marked grade areacceptable.

Test Result: Grade

-   Cloudiness more than 50% of the whole: (Inferior)-   Cloudiness more than 10% of the whole and not more than 50%-   Cloudiness more than 2% of the whole and not more than 10%-   Very slight cloudiness (not more than 2% of the whole)-   No change: (Superior)    The investigation results are given in Tables 21 and 22.

From Tables 19 to 22, the following facts are found for either can type.

Invention examples 1 to 7 are films in which R1 layer is a resin layerin which modified polyolefin resin specified in the present invention isdispersed in polyester resin in which the mixing ratio of polyethyleneterephthalate to polybutylene terephthalate is changed variously and R0layer is a resin layer of polyethylene terephthalate specified in thepresent invention, and invention examples 38 to 44 in which these filmsare laminated under the laminating conditions of the present inventionexhibit very high formability, impact resistance, adhesion, andcloudiness resistance. Among these, invention example 43 in which thefilm of invention example 6 using polyester resin having a lowpercentage of polybutylene terephthalate is laminated and inventionexample 44 in which the film of invention example 7 further usinghomopolyethylene terephthalate is laminated have a tendency for adhesionafter heating and cloudiness resistance after retorting to bedeteriorated as the percentage of polybutylene terephthalate becomeslow, but still have high performance as a whole. Also, invention example45 in which the film of invention example 8 using polyethyleneterephthalate in which polyester resin is copolymerized by isophthalicacid is laminated has a tendency for adhesion after heating andcloudiness resistance after retorting to be deteriorated slightly, butstill have high performance as a whole. On the other hand, inventionexamples 38 and 39 in which the films of invention examples 1 and 2having a very high percentage of polybutylene terephthalate arelaminated have a tendency toward deteriorated adhesion after heatingbecause the melting point is slightly low, but have high performance asa whole. On the other hand, comparative examples 1 to 8 are examples offilms in which polyester resin in which the mixing ratio of polyethyleneterephthalate to polybutylene terephthalate is changed variously doesnot contain polyolefin resin. Comparative examples 23 to 30 in whichthese films are laminated especially have a low level of impactresistance.

Invention examples 9 to 13 are films using mixed resin in which varioustypes of polyolefin resins are dispersed in polyester resin as R1 layer,and invention examples 46 to 50 in which these films are laminatedexhibit high formability, impact resistance, adhesion, and cloudinessresistance. However, invention example 46 in which the film of inventionexample 9 using polyolefin resin having a slightly high percentage offunctional group derived from carboxylic acid is laminated and inventionexample 50 in which the film of invention example 13 using polyolefinresin having a slightly high glass-transition temperature is laminatedhave a tendency toward slightly deteriorated low-temperature impactresistance. On the other hand, comparative examples 13 to 15 are mixedresins in which polyolefin resin containing a functional group derivedfrom carboxylic acid whose percentage deviates from the range of thepresent invention is dispersed in polyester resin, and comparativeexamples 35 to 37 in which these mixed resins are laminated havedeteriorated formability and impact resistance.

Comparative example 16 is a film in which modified polyolefin resin withgroup derived from carboxylic acid and polyester resin are simply mixedwith each other, and comparative example 38 in which this film islaminated has greatly deteriorated formability and impact resistancebecause modified polyolefin resin is not dispersed in polyester resin ina fine granular form.

Invention examples 14 to 21 are films in which the blending ratio anddispersion state of modified polyolefin resin in polyester resin arechanged variously in the range of the present invention, and inventionexamples 51 to 58 in which the films are laminated under the laminatingconditions of the present invention exhibit high formability, impactresistance, adhesion, and cloudiness resistance. However, inventionexample 51 in which the film of invention example 14 containing a smallamount of dispersed modified polyolefin resin is laminated and inventionexample 57 in which the film of invention example 20 containing a verylarge amount of modified polyolefin resin is laminated have a tendencytoward slightly deteriorated low-temperature impact resistance.

On the other hand, comparative examples 9 to 12 are films in which theblending ratio of modified polyolefin resin in polyester resin does notmeet the requirement of the present invention, and comparative examples31 to 34 in which the films are laminated under the laminatingconditions of the present invention have greatly deterioratedformability or impact resistance. Comparative examples 31 and 32 inwhich the films of comparative examples 9 and 10 containing a smallamount of dispersed modified polyolefin resin are laminated have greatlydeteriorated room-temperature impact resistance, and comparativeexamples 33 and 34 in which the films of comparative examples 11 and 12containing a large amount of modified polyolefin resin are laminatedhave greatly deteriorated formability.

Invention examples 33 to 37 are films in which titanium dioxide pigmentis mixed with a mixed resin of modified polyolefin resin and polyesterresin, and invention examples 70 to 74 in which the films are laminatedunder the laminating conditions of the present invention exhibit highformability, impact resistance, adhesion, and cloudiness resistance, andalso provide a white uniform color tone. However, invention example 70in which the film of invention example 33 in which the added amount ofpigment is smaller than a desired range is laminated has slightlyinsufficient opacifying property of color tone. On the other hand,invention example 74 in which the film of invention example 37 in whichthe added amount of pigment is larger than a desired range is laminatedhas slightly deteriorated formability.

Invention examples 22 to 28 are films in which the thickness of eachlayer of film is changed, and invention examples 59 to 65 in which thefilms are laminated under the laminating conditions of the presentinvention exhibit high formability, impact resistance, adhesion, andcloudiness resistance. Since the invention examples 22 and 28 are filmsin which the total thickness of film exceeds the desired range of thepresent invention, invention examples 59 and 65 in which the films arelaminated have slightly deteriorated formability and impact resistanceas compared with the film having a desired thickness. On the other hand,invention examples 17a to 20a are films in which the thickness orthickness ratio of each layer of film deviates from the desired range ofthe present invention, and invention examples 39a to 42a in which thefilms are laminated have slightly deteriorated balance of formabilityand impact resistance as compared with invention examples 22 to 28.

Invention examples 41 and 75 to 78 are films obtained by changing thelaminating conditions of the film of invention example 4 in the range ofthe present invention. If the conditions are within the range of thepresent invention, high formability, impact resistance, adhesion, andcloudiness resistance are exhibited regardless of the laminatingtemperature. On the other hand, in comparative example 39, the film ofinvention example 4 was laminated under conditions lower than the lowerlimit of laminating temperature range of the present invention, so thatthe film did not adhere to a steel sheet, and therefore evaluation couldnot be made. On the other hand, in comparative example 40, the film ofinvention example 4 was laminated under conditions exceeding the upperlimit of laminating temperature range of the present invention, so thatthe film fused to a laminate roll, and therefore evaluation could not bemade.

Invention examples 29 to 31 are films in which a lubricant, free radicalinhibitor, and compatibilizing agent are mixed, respectively, in a mixedresin of modified polyolefin resin and polyester resin of the presentinvention, and invention examples 66 to 68 in which the films arelaminated under the laminating conditions of the present inventionexhibit high formability, impact resistance, adhesion, and cloudinessresistance. Further, invention examples 66 to 68 also have lubricity,free radical deterioration resistance, and compatibility depending onthe function of added additive, and in particular, invention example 68exhibits excellent low-temperature impact-resistance.

Invention example 32 is a film of the present invention that ismanufactured by the two-axis stretching method, and invention examples69 and 79 in which the film is laminated exhibit high performance.Invention example 79, which has a plane orientation coefficient of0.015, exhibits a slightly deteriorated formability. Invention example69, which has a plane orientation coefficient in the range of theseventh invention, exhibits very high formability and impact resistance.

Invention examples 21a and 22a are films using polyester resin otherthan the present invention as R0 layer, and invention examples 43a and44a in which the films are laminated have slightly deteriorated adhesionafter heating.

TABLE 19 R1 layer Entire film Polyolefin resin Thickness Weightpercentage Blending Volume Number of grains ratio of Polyester offunctional ratio in percentage of with diameter of R0 layer Film R1layer resin group derived entire grains with 0.1 to 5 μm in FilmPolyester Film thickness to R0 Pigment Sample Resin Resin fromcarboxylic Tg resin diameter of 0.1 cube with one side thickness resinthickness (R1 + R0) layer Content film type Additive type acid (wt %) (°C.) (wt %) to 5 μm (vol %) of 10 μm (grains) (μm) Resin type (μm) (μm)R1/R0 Type (wt %) *1) Stretching Invention PET/ None EM4 8 <−30 15 122000 22 PET 4 26 5.5 None 0 Non- example 1 PBT(90) stretched InventionPET/ None EM4 8 <−30 15 12 2000 22 PET 4 26 5.5 None 0 Non- example 2PBT(80) stretched Invention PET/ None EM4 8 <−30 15 12 2000 22 PET 4 265.5 None 0 Non- example 3 PBT(70) stretched Invention PET/ None EM4 8<−30 15 12 2000 22 PET 4 26 5.5 None 0 Non- example 4 PBT(60) stretchedInvention PET/ None EM4 8 <−30 15 12 2000 22 PET 4 26 5.5 None 0 Non-example 5 PBT(40) stretched Invention PET/ None EM4 8 <−30 15 12 2000 22PET 4 26 5.5 None 0 Non- example 7 PBT(20) stretched Invention PET NoneEM4 8 <−30 15 12 2000 22 PET 4 26 5.5 None 0 Non- example 7 stretchedInvention PET/I None EM4 8 <−30 15 12 2000 22 PET 4 26 5.5 None 0 Non-example 8 (10) stretched Invention PET/ None EM2 18 <−30 15 13 500 22PET 4 26 5.5 None 0 Non- example 9 PBT(60) stretched Invention PET/ NoneEM4 8 <−30 15 12 2000 22 PET 4 26 5.5 None 0 Non- example 10 PBT(60)stretched Invention PET/ None EM5 7 <−30 15 12 2000 22 PET 4 26 5.5 None0 Non- example 11 PBT(60) stretched Invention PET/ None EM6 5 <−30 15 122000 22 PET 4 26 5.5 None 0 Non- example 12 PBT(60) stretched InventionPET/ None EM8 6 20 15 12 2000 22 PET 4 26 5.5 None 0 Non- example 13PBT(60) stretched Invention PET/ None EM3 11 <−30 5 3 3 22 PET 4 26 5.5None 0 Non- example 14 PBT(60) stretched Invention PET/ None EM3 11 <−305 5 70 22 PET 4 26 5.5 None 0 Non- example 15 PBT(60) stretchedInvention PET/ None EM3 11 <−30 10 8 30 22 PET 4 26 5.5 None 0 Non-example 16 PBT(60) stretched Invention PET/ None EM3 11 <−30 10 10 25022 PET 4 26 5.5 None 0 Non- example 17 PBT(60) stretched Invention PET/None EM3 11 <−30 15 15 500 22 PET 4 26 5.5 None 0 Non- example 18PBT(60) stretched Invention PET/ None EM3 11 <−30 15 18 20000 22 PET 426 5.5 None 0 Non- example 19 PBT(60) stretched Invention PET/ None EM311 <−30 20 22 200000 22 PET 4 26 5.5 None 0 Non- example 20 PBT(60)stretched Invention PET/ None EM3 11 <−30 28 20 8000 22 PET 4 26 5.5None 0 Non- example 21 PBT(60) stretched Invention PET/ None EM6 5 <−3015 12 2000 10 PET 1 11 10.0 None 0 Non- example 22 PBT(60) stretchedInvention PET/ None EM6 5 <−30 15 12 2000 15 PET 3 18 5.0 None 0 Non-example 23 PBT(60) stretched Invention PET/ None EM6 5 <−30 15 12 200020 PET 3 23 6.7 None 0 Non- example 24 PBT(60) stretched Invention PET/None EM6 5 <−30 15 12 2000 25 PET 5 30 5.0 None 0 Non- example 25PBT(60) stretched Invention PET/ None EM6 5 <−30 15 12 2000 30 PET 4 347.5 None 0 Non- example 26 PBT(60) stretched Invention PET/ None EM6 5<−30 15 12 2000 45 PET 5 50 9.0 None 0 Non- example 27 PBT(60) stretchedInvention PET/ None EM6 5 <−30 15 12 2000 50 PET 10 60 5.0 None 0 Non-example 28 PBT(60) stretched Invention PET/ *2) 0.3 EM3 11 <−30 15 122000 22 PET 4 26 5.5 None 0 Non- example 29 PBT(60) wt % stretchedInvention PET/ *3) 0.1 EM3 11 <−30 15 12 2000 22 PET 4 26 5.5 None 0Non- example 30 PBT(60) wt % stretched Invention PET/ *4) 3 EM3 11 <−3015 12 2000 22 PET 4 26 5.5 None 0 Non- example 31 PBT(60) wt % stretched*1) Pigment content means weight percentage (wt %) of pigment withrespect to total film amount of entire resin and pigment. Pigment isadded to R1 layer. *2) Silicone of lubricant is added by 3 weight partto 100 weight part of mixed resin. *3) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane of free radicalinhibitor is added by 0.1 weight part to 100 weight part of mixed resin.*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) ofcompatibilizing agent is added by 3 weight part to 100 weight part ofmixed resin

TABLE 20 R1 layer Entire film Polyolefin resin Thickness Weightpercentage Blending Volume Number of grains ratio of Polyester offunctional ratio in percentage of with diameter of R0 layer Film R1layer resin group derived entire grains with 0.1 to 5 μm in FilmPolyester Film thickness to R0 Pigment Sample Resin Resin fromcarboxylic Tg resin diameter of 0.1 cube with one side thickness resinthickness (R1 + R0) layer Content film type Additive type acid (wt %) (°C.) (wt %) to 5 μm (vol %) of 10 μm (grains) (μm) Resin type (μm) (μm)R1/R0 Type (wt %) *1) Stretching film type Additive type acid (wt %) (°C.) (wt %) to 5 μm (vol %) of 10 μm (grains) (μm) Resin type (μm) (μm)R1/R0 Type (wt %) *1) Stretching Invention PET/ None EM4 8 <−30 15 122000 22 PET 4 26 5.5 None 0 Two-axis example 32 PBT(60) stretchedInvention PET/ None EM5 7 <−30 15 12 2000 22 PET 4 26 5.5 TiO₂ 3 Non-example 33 PBT(60) stretched Invention PET/ None EM5 7 <−30 15 12 200022 PET 4 26 5.5 TiO₂ 7 Non- example 34 PBT(60) stretched Invention PET/None EM5 7 <−30 15 12 2000 22 PET 4 26 5.5 TiO₂ 15 Non- example 35PBT(60) stretched Invention PET/ None EM5 7 <−30 15 12 2000 22 PET 4 265.5 TiO₂ 30 Non- example 36 PBT(60) stretched Invention PET/ None EM5 7<−30 15 12 2000 22 PET 4 26 5.5 TiO₂ 50 Non- example 37 PBT(60)stretched Comparative PET/ None None — — 0 0 0 22 PET 4 26 5.5 None 0Non- example 1 PBT(90) stretched Comparative PET/ None None — — 0 0 0 22PET 4 26 5.5 None 0 Non- example 2 PBT(80) stretched Comparative PET/None None — — 0 0 0 22 PET 4 26 5.5 None 0 Non- example 3 PBT(70)stretched Comparative PET/ None None — — 0 0 0 22 PET 4 26 5.5 None 0Non- example 4 PBT(60) stretched Comparative PET/ None None — — 0 0 0 22PET 4 26 5.5 None 0 Two-axis example 5 PBT(60) stretched Comparati34PET/ None None — — 0 0 0 22 PET 4 26 5.5 None 0 Non- example 6 PBT(40)stretched Comparative PET/ None None — — 0 0 0 22 PET 4 26 5.5 None 0Non- example 7 PBT(20) stretched Comparative PET None None — — 0 0 0 22PET 4 26 5.5 None 0 Non- example 8 stretched Comparative PET/ None EM311 <−30 2 2 3 22 PET 4 26 5.5 None 0 Non- example 9 PBT(60) stretchedComparative PET/ None EM3 11 <−30 2 2 45 22 PET 4 26 5.5 None 0 Non-example 10 PBT(60) stretched Comparative PET/ None EM3 11 <−30 35 2815000 22 PET 4 26 5.5 None 0 Non- example 11 PBT(60) stretchedComparative PET/ None EM3 11 <−30 35 28 120000 22 PET 4 26 5.5 None 0Non- example 12 PBT(60) stretched Comparative PET/ None EM1 21 <−30 1514 40 22 PET 4 26 5.5 None 0 Non- example 13 PBT(60) stretchedComparative PET/ None EM7 1 <−30 15 3 20 22 PET 4 26 5.5 None 0 Non-example 14 PBT(60) stretched Comparative PET/ None EPR 0 <−30 15 1 5 22PET 4 26 5.5 None 0 Non- example 15 PBT(60) stretched Comparative PET/None EM5 7 <−30 15 Not dispersed Not dispersed 22 PET 4 26 5.5 None 0Non- example 16 PBT(60) in fine grains in fine grains stretchedInvention PET/ None EM6 5 <−30 15 12 2000 7 PET 1 8 7.0 None 0 Non-example 17a PBT(60) stretched Invention PET/ None EM6 5 <−30 15 12 200060 PET 10 70 6.0 None 0 Non- example 18a PBT(60) stretched InventionPET/ None EM6 5 <−30 15 12 2000 20 PET 1.5 21.5 13.3 None 0 Non- example19a PBT(60) stretched Invention PET/ None EM6 5 <−30 15 12 2000 15 PET 823 1.9 None 0 Non- example 20a PBT(60) stretched Invention PET/ None EM48 <−30 15 12 2000 22 PET/PBT 4 26 5.5 None 0 Non- example 21a PBT(60)(60) stretched Invention PET/ None EM4 8 <−30 15 12 2000 22 PET/I 4 265.5 None 0 Non- example 22a PBT(60) (10) stretched *1) Pigment contentmeans weight percentage (wt %) of pigment with respect to total filmamount of entire resin and pigment. Pigment is added to R1 layer.

TABLE 21 Melting Thin-wall deep drawn can Drawn and ironed can (DI can)point of Impact Impact Cloudiness Cloudiness Laminated R1 layerLaminating Plane resistance resistance Adhesion Adhesion of ImpactImpact Adhesion Adhesion of metal Sample polyester temp. orientationForma- (room (low after after retorted Forma- resistance resistanceafter after retorted sheet film resin (° C.) (° C.) coefficient bilitytemp.) temp.) forming heating film bility (room temp.) (low temp.)forming heating film Invention Invention 215 200 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 38 example 1 Invention Invention 220 210 0 ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 39 example 2 Invention Invention 230 210 0⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 40 example 3 Invention Invention235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 41 example 4 InventionInvention 240 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 42 example 5Invention Invention 245 225 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 43example 6 Invention Invention 255 235 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 44 example 7 Invention Invention 230 210 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 45 example 8 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 46 example 9 Invention Invention 235 215 0⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 47 example 10 InventionInvention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 48 example11 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example49 example 12 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 50 example 13 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 51 example 14 Invention Invention 235 215 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 52 example 15 Invention Invention235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 53 example 16Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 54example 17 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 55 example 18 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 56 example 19 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 57 example 20 Invention Invention 235215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 58 example 21 InventionInvention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 59 example22 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ exampleexample 60 23 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example example 61 24 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 62 25 Invention Invention 235 215 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 63 26 Invention Invention235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 64 27Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ exampleexample 65 28 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example example 66 29 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 67 30 Invention Invention 235 215 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example example 68 31

TABLE 22 Melting Thin-wall deep drawn can Drawn and ironed can (DI can)point of Impact Impact Cloudiness Cloudiness Laminated R1 layerLaminating Plane resistance resistance Adhesion Adhesion of ImpactImpact Adhesion Adhesion of metal Sample polyester temp. orientationForma- (room (low after after retorted Forma- resistance resistanceafter after retorted sheet film resin (° C.) (° C.) coefficient bilitytemp.) temp.) forming heating film bility (room temp.) (low temp.)forming heating film Invention Invention 235 215 0.005 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 69 example 32 Invention Invention 235 215 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 70 example 33 Invention Invention235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 71 example 34Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 72example 35 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 73 example 36 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 74 example 37 Invention Invention 235 260 0 ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 75 example 4 Invention Invention 235 2300 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 76 example 4 InventionInvention 235 190 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 77 example 4Invention Invention 235 170 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 78example 4 Invention Invention 235 200 0.015 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 79 example 32 Comparative Comparative 215 200 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 23 example 1 Comparative Comparative 220 2100 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 24 example 2 ComparativeComparative 230 210 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 25 example3 Comparative Comparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 26 example 4 Comparative Comparative 240 220 0.015 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 27 example 5 Comparative Comparative 245 2250 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 28 example 6 ComparativeComparative 255 235 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 29 example7 Comparative Comparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 30 example 8 Comparative Comparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 31 example 9 Comparative Comparative 235 215 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 32 example 10 ComparativeComparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 33 example11 Comparative Comparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 34 example 12 Comparative Comparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 35 example 13 Comparative Comparative 235 215 0⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 36 example 14 ComparativeComparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 37 example15 Comparative Comparative 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 38 example 16 Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 39a example 17a Invention Invention 235 215 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 40a example 18a Invention Invention235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 41a example 19aInvention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example42a example 20a Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ◯ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ◯⊚⊚ example 43a example 21a Invention Invention 235 215 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ◯ ⊚⊚⊚ ⊚ ⊚⊚⊚ ⊚ ◯ ⊚⊚ example 44a example 22a Comparative Invention 235 270 — —— — — — — — — — — — — example 39 example 4 Comparative Invention 235 160— — — — — — — — — — — — — example 40 example 4

Example 6

Modified polyolefin resin with group derived from carboxylic acid havinga primary grain diameter of 0.3 μm, which was a starting raw material,was cold blended with polyester resin in a blending ratio given inTables 23 and 24 by using a tumbler blender, and then the blended resinwas melted and kneaded at 260° C. by using a two-axis extruding machine,by which a raw material pellet of polyester resin in which modifiedpolyolefin resin was dispersed was obtained. In the tables, the resintype corresponding to the symbol of resin type of polyester resin andresin type of polyolefin resin is the same as that described in Example5.

As a metal sheet, as in Example 5, a tin-free steel (hereinafterabbreviated to TFS) with a thickness of 0.18 mm for thin-wall deep drawncan and 0.23 mm for DI can, which had a degree of temper of DR9,metallic chromium layer of 80 mg/m², and chromium oxide layer of 15mg/m² (metallic chromium conversion), was used, by which a both-sidelaminated metal sheet was obtained by a method in which the raw materialresin pellet was inserted in a one-axis extruding machine as a resin forR1 layer, a resin for R0 layer was inserted in a separate extrudingmachine and simultaneously melted and extruded, molten resin was put ina T die by a combining adapter, two-layer molten resin was extrudeddirectly onto one surface of the metal sheet, the extruded resin wasonce cooled while being held adherently between two rolls, andimmediately after the resin was laminated on the opposite surface in thesame manner, the resin laminated metal sheet was cooled rapidly inwater. The temperature of metal sheet at the laminating time was 230° C.The lip opening width of T die was adjusted so that the thickness ofresin film was 9.5 to 70 μm. The type of sample resin and the resinmelting temperature at the laminating time are given in Tables 23 and24. The used polyester resin and modified polyolefin resin with groupderived from carboxylic acid are the same as those used in Example 5.

Pelletized modified polyolefin resin with group derived from carboxylicacid, which was a starting raw material, was mixed with polyester resinin a blending ratio given in comparative example 61 in Table 25, themixed resin was melted and kneaded at 265° C. by using a one-axisextruding machine, and the obtained mixed resin of modified polyolefinresin and polyester resin was extruded from a T die as R1 layer, bywhich the resin that had been directly extruded to a thickness of 26 μmwas laminated to the TFS.

All of the grain diameter of modified polyolefin resin dispersed inresin film, various temperatures in the table, and the method formeasuring the plane orientation coefficient of resin laminated metalsheet are the same as those in Example 5. As in Example 5, a thin-walldeep drawn can or a DI can was manufactured from the laminated metalsheet obtained as described above, and the can was subjected tostraightening heat treatment to manufacture a sample can. Theformability, impact resistance, adhesion, and retort resistance of filmof the manufactured can body were investigated as in Example 5.

The investigation results are given in Tables 25 and 26.

From Tables 23 to 26, the following facts are found for either can type.

Invention examples 80 to 90 are films using a resin layer in whichmodified polyolefin resin specified in the present invention isdispersed in polyester resin in which the ratio of polyethyleneterephthalate to polybutylene terephthalate is changed variously as R1layer, and exhibit high formability, impact resistance, adhesion, andcloudiness resistance. Among these, invention example 89 using polyesterresin having a low percentage of polybutylene terephthalate andinvention example 90 further using homopolyethylene terephthalate have atendency for adhesion after heating and cloudiness resistance afterretorting to be deteriorated as the percentage of polybutyleneterephthalate becomes low, but still have high performance as a whole.Also, invention example 91 using polyethylene terephthalate in whichpolyester resin is copolymerized by isophthalic acid has a tendency foradhesion after heating and cloudiness resistance after retorting to bedeteriorated slightly, but still have high performance as a whole. Onthe other hand, invention examples 80 and 81 having a very highpercentage of polybutylene terephthalate have a tendency towarddeteriorated adhesion after heating because the melting point isslightly low, but have high performance as a whole. On the other hand,comparative examples 47 to 53 are examples in which polyester resin inwhich the mixing ratio of polyethylene terephthalate topolybutylene-terephthalate is changed variously does not containpolyolefin resin, and especially have a low level of impact resistance.

Invention examples 91 to 96 are films using mixed resin in which varioustypes of polyolefin resins are dispersed in polyester resin as R1 layer,and exhibit high formability, impact resistance, adhesion, andcloudiness resistance. However, invention example 92 using polyolefinresin having a slightly high percentage of functional group derived fromcarboxylic acid and invention example 96 using polyolefin resin having aslightly high glass-transition temperature have a tendency towardslightly deteriorated low-temperature impact resistance. On the otherhand, comparative examples 58 to 60 are mixed resins in which polyolefinresin containing a functional group derived from carboxylic acid whosepercentage deviates from the range of the present invention is dispersedin polyester resin, and have deteriorated formability and impactresistance.

Comparative example 61 is a resin in which modified polyolefin resinwith group derived from carboxylic acid and polyester resin are simplymixed with each other, and has greatly deteriorated formability andimpact resistance because modified polyolefin resin is not dispersed inpolyester resin in a fine granular form.

Invention examples 97 to 104 are resins in which the blending ratio anddispersion state of modified polyolefin resin in polyester resin arechanged variously in the range of the present invention, and exhibithigh formability, impact resistance, adhesion, and cloudinessresistance. However, invention example 97 containing a small amount ofdispersed modified polyolefin resin and invention example 103 containinga very large amount of modified polyolefin resin have a tendency towardslightly deteriorated low-temperature impact resistance.

On the other hand, comparative examples 54 to 57 are resins in which theblending ratio of modified polyolefin resin in polyester resin does notmeet the requirement of the present invention, and have greatlydeteriorated formability or impact resistance. Comparative examples 54and 55 containing a small amount of dispersed modified polyolefin resinhave greatly deteriorated room-temperature impact resistance, andcomparative examples 56 and 57 containing a large amount of modifiedpolyolefin resin have greatly deteriorated formability.

Invention examples 115 to 119 are resins in which titanium dioxidepigment is mixed with a mixed resin of modified polyolefin resin andpolyester resin, and exhibit high formability, impact resistance,adhesion, and cloudiness resistance, and also provide a white uniformcolor tone. However, invention example 115 in which the added amount ofpigment is smaller than a desired range has slightly insufficientopacifying property of color tone. On the other hand, invention example119 in which the added amount of pigment is larger than a desired rangehas slightly deteriorated formability.

Invention examples 105 to 111 are resins in which the thickness of eachlayer of film is changed, and exhibit high formability, impactresistance, adhesion, and cloudiness resistance. Since the inventionexamples 105 and 111 are resins in which the total thickness of filmexceeds the desired range of the present invention, both formability andimpact resistance are slightly deteriorated as compared with the resinhaving a desired film thickness. On the other hand, invention examples120 to 123 are resins in which the thickness or thickness ratio of eachlayer of film-deviates from the desired range of the present invention,and have slightly deteriorated balance of formability and impactresistance as compared with invention examples 105 to 111.

Invention examples 112 to 114 are resins in which a lubricant, freeradical inhibitor, and compatibilizing agent are mixed, respectively, ina mixed resin of modified polyolefin resin and polyester resin of thepresent invention, and exhibit high formability, impact resistance,adhesion, and cloudiness resistance. Further, invention examples 112 to114 also have lubricity, free radical deterioration resistance, andcompatibility depending on the function of added additive, and inparticular, invention example 114 exhibits excellent low-temperatureimpact resistance.

Invention examples 124 and 125 are resins using polyester resin otherthan the present invention as R0 layer, and have slightly deterioratedadhesion after heating.

TABLE 23 R1 layer Polyolefin resin Polyester resin Weight percentageBlending Melting of functional ratio in point of group derived fromentire Sample Resin polyester Resin carboxylic acid Tg resin film typeresin (° C.) Additive type (wt %) (° C.) (wt %) Invention PET/PBT(90)215 None EM4 8 <−30 15 example 80 Invention PET/PBT(80) 220 None EM4 8<−30 15 example 81 Invention PET/PBT(70) 230 None EM4 8 <−30 15 example82 Invention PET/PBT(60) 235 None EM4 8 <−30 15 example 83 InventionPET/PBT(60) 235 None EM4 8 <−30 15 example 84 Invention PET/PBT(60) 235None EM4 8 <−30 15 example 85 Invention PET/PBT(60) 235 None EM4 8 <−3015 example 86 Invention PET/PBT(60) 235 None EM4 8 <−30 15 example 87Invention PET/PBT(40) 240 None EM4 8 <−30 15 example 88 InventionPET/PBT(20) 245 None EM4 8 <−30 15 example 89 Invention PET 255 None EM48 <−30 15 example 90 Invention PET/I(10) 230 None EM4 8 <−30 15 example91 Invention PET/PBT(60) 235 None EM2 18 <−30 15 example 92 InventionPET/PBT(60) 235 None EM4 8 <−30 15 example 93 Invention PET/PBT(60) 235None EM5 7 <−30 15 example 94 Invention PET/PBT(60) 235 None EM6 5 <−3015 example 95 Invention PET/PBT(60) 235 None EM8 6 20 15 example 96Invention PET/PBT(60) 235 None EM3 11 <−30 5 example 97 InventionPET/PBT(60) 235 None EM3 11 <−30 5 example 98 Invention PET/PBT(60) 235None EM3 11 <−30 10 example 99 Invention PET/PBT(60) 235 None EM3 11<−30 10 example 100 Invention PET/PBT(60) 235 None EM3 11 <−30 15example 101 Invention PET/PBT(60) 235 None EM3 11 <−30 15 example 102Invention PET/PBT(60) 235 None EM3 11 <−30 20 example 103 InventionPET/PBT(60) 235 None EM3 11 <−30 28 example 104 Invention PET/PBT(60)235 None EM6 5 <−30 15 example 105 Invention PET/PBT(60) 235 None EM6 5<−30 15 example 106 Invention PET/PBT(60) 235 None EM6 5 <−30 15 example107 Invention PET/PBT(60) 235 None EM6 5 <−30 15 example 108 InventionPET/PBT(60) 235 None EM6 5 <−30 15 example 109 Invention PET/PBT(60) 235None EM6 5 <−30 15 example 110 Invention PET/PBT(60) 235 None EM6 5 <−3015 example 111 R1 layer Melting Polyolefin resin temp. of Volume Numberof grains R1 layer percentage of with diameter of R0 layer Pigment resinat grains with 0.1 to 5 μm in Polyester Content extrusion Samplediameter of 0.1 cube with one side resin (wt %) laminating film to 5 μm(vol %) of 10 μm (grains) Resin type Type *1) time (° C.) Invention 142500 PET None 0 245 example 80 Invention 14 2500 PET None 0 250 example81 Invention 14 2500 PET None 0 260 example 82 Invention 14 2500 PETNone 0 240 example 83 Invention 14 2500 PET None 0 250 example 84Invention 14 2500 PET None 0 265 example 85 Invention 14 2500 PET None 0280 example 86 Invention 14 2500 PET None 0 290 example 87 Invention 142500 PET None 0 270 example 88 Invention 14 2500 PET None 0 275 example89 Invention 14 2500 PET None 0 285 example 90 Invention 14 2500 PETNone 0 260 example 91 Invention 15 1000 PET None 0 265 example 92Invention 14 2500 PET None 0 265 example 93 Invention 14 2500 PET None 0265 example 94 Invention 14 2500 PET None 0 265 example 95 Invention 142500 PET None 0 265 example 96 Invention 4 4 PET None 0 265 example 97Invention 8 100 PET None 0 265 example 98 Invention 10 50 PET None 0 265example 99 Invention 12 500 PET None 0 265 example 100 Invention 18 800PET None 0 265 example 101 Invention 20 22000 PET None 0 265 example 102Invention 24 250000 PET None 0 265 example 103 Invention 22 10000 PETNone 0 265 example 104 Invention 14 2500 PET None 0 265 example 105Invention 14 2500 PET None 0 265 example 106 Invention 14 2500 PET None0 265 example 107 Invention 14 2500 PET None 0 265 example 108 Invention14 2500 PET None 0 265 example 109 Invention 14 2500 PET None 0 265example 110 Invention 14 2500 PET None 0 265 example 111 *1) Pigmentcontent means weight percentage (wt %) of pigment with respect to totalfilm amount of entire resin and pigment. Pigment is added to R1 layer.

TABLE 24 R1 layer Polyolefin resin Polyester resin Weight percentageBlending Melting of functional ratio in point of group derived fromentire Sample Resin polyester Resin carboxylic acid Tg resin film typeresin (° C.) Additive type (wt %) (° C.) (wt %) Invention PET/PBT(60)235 *2) EM3 11 <−30 15 example 112 0.3 wt % Invention PET/PBT(60) 235*3) EM3 11 <−30 15 example 113 0.1 wt % Invention PET/PBT(60) 235 *4)EM3 11 <−30 15 example 114   3 wt % Invention PET/PBT(60) 235 None EM5 7<−30 15 example 115 Invention PET/PBT(60) 235 None EM5 7 <−30 15 example116 Invention PET/PBT(60) 235 None EM5 7 <−30 15 example 117 InventionPET/PBT(60) 235 None EM5 7 <−30 15 example 118 Invention PET/PBT(60) 235None EM5 7 <−30 15 example 119 Comparative PET/PBT(90) 215 None None — —0 example 47 Comparative PET/PBT(80) 220 None None — — 0 example 48Comparative PET/PBT(70) 230 None None — — 0 example 49 ComparativePET/PBT(60) 235 None None — — 0 example 50 Comparative PET/PBT(40) 245None None — — 0 example 51 Comparative PET/PBT(20) 255 None None — — 0example 52 Comparative PET 235 None None — — 0 example 53 ComparativePET/PBT(60) 235 None EM3 11 <−30 2 example 54 Comparative PET/PBT(60)235 None EM3 11 <−30 2 example 55 Comparative PET/PBT(60) 235 None EM311 <−30 35 example 56 Comparative PET/PBT(60) 235 None EM3 11 <−30 35example 57 Comparative PET/PBT(60) 235 None EM1 21 <−30 15 example 58Comparative PET/PBT(60) 235 None EM7 1 <−30 15 example 59 ComparativePET/PBT(60) 235 None EPR 0 <−30 15 example 60 Comparative PET/PBT(60)235 None EM5 7 <−30 15 example 61 Invention PET/PBT(60) 235 None EM6 5<−30 15 example 120 Invention PET/PBT(60) 235 None EM6 5 <−30 15 example121 Invention PET/PBT(60) 235 None EM6 5 <−30 15 example 122 InventionPET/PBT(60) 235 None EM6 5 <−30 15 example 123 Invention PET/PBT(60) 235None EM4 8 <−30 15 example 124 Invention PET/PBT(60) 235 None EM4 8 <−3015 example 125 R1 layer Melting Polyolefin resin temp. of Volume Numberof grains R1 layer percentage of with diameter of R0 layer Pigment resinat grains with 0.1 to 5 μm in Polyester Content extrusion Samplediameter of 0.1 cube with one side resin (wt %) laminating film to 5 μm(vol %) of 10 μm (grains) Resin type Type *1) time (° C.) Invention 142500 PET None 0 265 example 112 Invention 14 2500 PET None 0 265 example113 Invention 14 2500 PET None 0 265 example 114 Invention 14 2500 PETTiO₃ 3 265 example 115 Invention 14 2500 PET TiO₂ 7 265 example 116Invention 14 2500 PET TiO₂ 15 265 example 117 Invention 14 2500 PET TiO₂30 265 example 118 Invention 14 2500 PET TiO₃ 50 265 example 119Comparative 0 0 PET None 0 245 example 47 Comparative 0 0 PET None 0 250example 48 Comparative 0 0 PET None 0 260 example 49 Comparative 0 0 PETNone 0 265 example 50 Comparative 0 0 PET None 0 275 example 51Comparative 0 0 PET None 0 285 example 52 Comparative 0 0 PET None 0 265example 53 Comparative 3 5 PET None 0 265 example 54 Comparative 3 50PET None 0 265 example 55 Comparative 30 20000 PET None 0 265 example 56Comparative 30 135000 PET None 0 265 example 57 Comparative 16 50 PETNone 0 265 example 58 Comparative 4 40 PET None 0 265 example 59Comparative 1 4 PET None 0 265 example 60 Comparative Not dispersed Notdispersed PET None 0 265 example 61 in fine grains in fine grainsInvention 14 2500 PET None 0 265 example 120 Invention 14 2500 PET None0 265 example 121 Invention 14 2500 PET None 0 265 example 122 Invention14 2500 PET None 0 265 example 123 Invention 14 2500 PET/PBT(60) None 0265 example 124 Invention 14 2500 PET/I(10) None 0 265 example 125 *1)Pigment content means weight percentage (wt %) of pigment with respectto total film amount of entire resin and pigment. Pigment is added to R1layer. *2) Silicone of lubricant is added by 3 weight part to 100 weightpart of mixed resin. *3) Tetrakis-[Methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane of free radicalinhibitor is added by 0.1 weight part to 100 weight part of mixed resin.*4) Bond First 20B (manufactured by Sumitomo Chemical Co., Ltd.) ofcompatibilizing agent is added by 3 weight part to 100 weight part ofmixed resin.

TABLE 25 Investigation result Resin film thickness Thin-wall deep drawncan Drawn and ironed can (DI can) Extrusion Total film ThicknessCloudiness Cloudiness laminated R1 R0 thickness ratio of R1 ImpactImpact Adhesion Adhesion of Impact Impact Adhesion Adhesion of metallayer layer (R1 + R0) layer to R0 resistance resistance after afterretorted resistance resistance after after retorted sheet (μm) (μm) (μm)layer R1/R0 Formability (room temp.) (low temp.) forming heating filmFormability (room temp.) (low temp.) forming heating film Invention 22 426 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 80 Invention 22 4 26 5.5⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 81 Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 82 Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 83 Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ example 84 Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 85 Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example86 Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 87Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 88Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 89Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 90Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 91Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 92Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 93Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 94Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 95Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 96Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 97Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 98Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 99Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 100Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 101Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 102Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 103Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 104Invention 10 1 11 10.0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 105Invention 15 3 18 5.0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 106Invention 20 3 23 6.7 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 107Invention 25 5 30 5.0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 108Invention 30 4 34 7.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 109Invention 45 5 50 9.0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 110Invention 50 10 60 5.0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 111

TABLE 26 Investigation result Resin film thickness Thin-wall deep drawncan Drawn and ironed can (DI can) Extrusion Total film ThicknessCloudiness Cloudiness laminated R1 R0 thickness ratio of R1 ImpactImpact Adhesion Adhesion of Impact Impact Adhesion Adhesion of metallayer layer (R1 + R0) layer to R0 resistance resistance after afterretorted resistance resistance after after retorted sheet (μm) (μm) (μm)layer R1/R0 Formability (room temp.) (low temp.) forming heating filmFormability (room temp.) (low temp.) forming heating film Invention 22 426 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 112 Invention 22 4 26 5.5⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 113 Invention 22 4 26 5.5 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 114 Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 115 Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 116 Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 117 Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ example 118 Invention 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 119 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 47 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 48 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 49 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 50 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 51 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 52 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 53 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 54 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 55 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 56 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 57 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 58 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 59 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 60 Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 61 Comparative 7 1 8 7.0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example120 Comparative 60 10 70 6.0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 121Comparative 20 1.5 21.5 13.3 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 122Comparative 15 8 23 1.9 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 123Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ◯ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ◯ ⊚⊚ example 124Comparative 22 4 26 5.5 ⊚ ⊚ ⊚⊚⊚ ⊚ ◯ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ◯ ⊚⊚ example 125

Example 7

As a resin raw material for R1 layer, modified polyolefin resin withgroup derived from carboxylic acid was cold blended with polyester resinin a blending ratio given in Tables 27 to 29 by using a tumbler blender,and then the blended resin was melted and kneaded at 270° C. by using atwo-axis extruding machine, by which a raw material pellet of polyesterresin in which modified polyolefin resin was dispersed was obtained. Theraw material resin pellet was inserted in a one-axis extruding machine,and on the other hand, modified polyolefin resin, which was a resin rawmaterial for R2 layer, was inserted in a separate one-axis extrudingmachine, and each of molten resins was introduced into a multi-manifoldtype T die and extruded in two layers while the film thickness of R1 andR2 layers was controlled by the discharge amount of molten resin fromthe extruding machine, by which a resin film was manufacturedcontinuously while being cooled by the surface of a rotating metallicroll.

Also, in the case of three-layer construction having R0 layer, polyesterresin, which was a resin raw material for R0 layer, was inserted in aseparate one-axis extruding machine, and each of molten resins wasintroduced into a multi-manifold type T die and extruded in three layerswhile the film thickness of R0, R1 and R2 layers was controlled by thedischarge amount of molten resin from the extruding machine, by which aresin film was manufactured continuously while being cooled by thesurface of a rotating metallic roll.

The used polyester resin and modified polyolefin resin with groupderived from carboxylic acid were as follows: Polyester resin

(1) PET: Polyethylene terephthalate resin, intrinsic viscosity: 0.62dl/g

(2) PET/I: Isophthalic acid copolymerized-polyethylene terephthalateresin with a ratio of terephthalic acid to isophthalic acid of 90:10,intrinsic viscosity: 0.62 dl/g

(3) PET/PBT: Mixed resin with a ratio of polyethylene terephthalate topolybutylene terephthalate of 40:60, intrinsic viscosity: 0.6 dl/g

(4) PET/AD: Adipic acid copolymerized polyethylene terephthalate resinwith a ratio of terephthalic acid to adipic acid of 80:20, intrinsicviscosity: 0.6 dl/g

2. Modified Polyolefin Resin with Group Derived from Carboxylic Acid

(1) EM1: Polymethylmethacrylate-(ethylene-ethyl acrylate copolymer)graft copolymer (Modiper A5200 manufactured by NOF Corp.), weight ratio(carboxylic acid conversion) of functional group derived from carboxylicacid: 21 wt %, glass-transition temperature: −30° C. or lower

(2) EM2: Polymethyl methacrylate-(ethylene-ethyl acrylate-maleicanhydride copolymer) graft copolymer (Modiper A8200 manufactured by NOFCorp.), weight ratio (carboxylic acid conversion) of functional groupderived from carboxylic acid: 18 wt %, glass-transition temperature:−30° C. or lower

(3) EM3: Ethylene-ethyl acrylate-maleic anhydride copolymer (BondineHX8290 manufactured by Sumitomo Chemical Co., Ltd.), weight ratio(carboxylic acid conversion) of functional group derived from carboxylicacid: 11 wt %, glass-transition temperature: −30° C. or lower

(4) EM4: Ethylene-methacrylic acid copolymer (Nucrel N1560 manufacturedby Mitsui-DuPont Polychemical Co., Ltd.), weight ratio (carboxylic acidconversion) of functional group derived from carboxylic acid: 8 wt %,glass-transition temperature: −30° C. or lower

(5) EM5: 50% Zn neutralized substance of ethylene-methacrylic acidcopolymer (Nucrel N1560 manufactured by Mitsui-DuPont Polychemical Co.,Ltd. neutralized partially by Zn), weight ratio (carboxylic acidconversion) of functional group derived from carboxylic acid: 7 wt %,glass-transition temperature: −30° C. or lower

(6) EM6: 60% Zn neutralized substance of ethylene-methacrylic acidcopolymer (Himilan 1557 manufactured by Mitsui-DuPont Polychemical Co.,Ltd.), weight ratio (carboxylic acid conversion) of functional groupderived from carboxylic acid: 5 wt %, glass-transition temperature: −30°C. or lower

(7) EM7: Ethylene-methacrylic acid copolymer (Nucrel NO200H manufacturedby Mitsui-DuPont Polychemical Co., Ltd.), weight ratio (carboxylic acidconversion) of functional group derived from carboxylic acid: 1 wt %,glass-transition temperature: −30° C. or lower

(8) EM8: Polystyrene-(ethylene-ethyl acrylate copolymer) graft copolymer(Modiper A5100 manufactured by NOF Corp.), weight ratio (carboxylic acidconversion) of functional group derived from carboxylic acid: 6 wt %,glass-transition temperature: 20° C.

(9) EPR: Ethylene-propylene rubber (EP07P manufactured by JSR Corp.),weight ratio (carboxylic acid conversion) of functional group derivedfrom carboxylic acid: 0 wt %, glass-transition temperature: −30° C. orlower

Furthermore, as a resin raw material, a commercially available resin(Sealer PT4274 manufactured by Mitsui-DuPont Polychemical Co., Ltd.)that had been pelletized in advance in a state in which modifiedpolyolefin resin with group derived from carboxylic acid was dispersedin polyester resin was inserted in a one-axis extruding machine in theblending ratio shown in invention examples 41 and 46 in Table 28, and onthe other hand, modified polyolefin resin, which was a resin rawmaterial for R2 layer, was inserted in a separate one-axis extrudingmachine, and each of molten resins was introduced into a multi-manifoldtype T die and extruded in two layers while the film thickness of R1 andR2 layers was controlled by the discharge amount of molten resin fromthe extruding machine, by which a resin film was manufacturedcontinuously while being cooled by the surface of a rotating metallicroll. In the case of three-layer construction having R0 layer, polyesterresin, which was a resin raw material for R0 layer, was inserted in aseparate one-axis extruding machine, and each of molten resins wasintroduced into a multi-manifold type T die and extruded in three layerswhile the film thickness of R0, R1 and R2 layers was controlled by thedischarge amount of molten resin from the extruding machine, by which aresin film was manufactured continuously while being cooled by thesurface of a rotating metallic roll.

A resin laminated metal sheet was obtained by a thermo-compressionbonding method in which the resin film obtained as described above washot-pressed on both surfaces of a tin-free steel (hereinafterabbreviated to TFS) heated by an induction heating system, and then thelaminated-metal sheet was rapidly cooled in water. The metal sheettemperature at the laminating time (laminating temperature) is given inTables 30 and 31. The thickness of TFS was 0.18 mm for thin-wall deepdrawn can and 0.23 mm for DI can, the degree of temperature was DR9 forboth cans, and the coating amount of metallic chromium and chromiumoxide of surface chrome plating layer were 80 mg/m² and 15 mg/m²(metallic chromium conversion), respectively.

The grain diameter of modified polyolefin resin dispersed in R1 layer ofresin film, various temperatures in the table, and the plane orientationcoefficient of resin laminated metal sheet were measured by the samemethod as that in Example 1.

Further, a thin-wall deep drawn can or a DI can was manufactured fromthe laminated metal sheet obtained as described above, and the can wassubjected to straightening heat treatment to manufacture a sample can.The formability, impact resistance (room temperature, low temperature),adhesion after forming, adhesion after heating, and flavor property offilm of the manufactured can body were investigated.

The following is a detailed description of the investigation method.

1. Evaluation by Thickness-decreasing Deep Drawing

1-1 Can Manufacturing

A resin laminated metal sheet was subjected to first-stage drawing andredrawing under the following conditions, by which a thin-wall deepdrawn can was obtained.

-   First-stage drawing    -   Blank diameter . . . 150 to 160 mm    -   First-stage drawing . . . drawing ratio: 1.65-   Redrawing    -   Primary redrawing . . . drawing ratio: 1.25    -   Secondary redrawing . . . drawing ratio: 1.25    -   Radius of curvature of die corner in redrawing process . . . 0.4        mm    -   Load for pressing wrinkle at the time of redrawing . . . 39227N        (4000 kg)-   Average thickness decreasing percentage of can sidewall    -   45 to 60% with respect to thickness of resin laminated metal        sheet before forming        1-2 Straightening Heat Treatment

Forming strain of film caused by can manufacturing was removed bykeeping the can in a thermal environment of film melting point minus 15°C. for 30 seconds and then by rapidly cooling it.

(1) Formability

Evaluation was made as described below by the limit of capability formanufacturing can without film failure. Grades not lower than ◯ markedgrade are acceptable.

Limit of forming (thickness decreasing percentage): Grade

-   Incapable of forming at thickness decreasing percentage of 45%:    (Inferior)-   Capable of forming up to thickness decreasing percentage of 45%-   Capable of forming up to thickness decreasing percentage of 50%-   Capable of forming up to thickness decreasing percentage of 55%-   Capable of forming up to thickness decreasing percentage of 60%:    (Superior)    (2) Evaluation of Room-temperature and Low-temperature Impact    Resistance

A can body (thickness decreasing percentage: 55%) subjected tostraightening heat treatment was necked, and the can body was filledwith distilled-water. After a lid was installed and tightened, an ironball of 0.5 kg was dropped from a height of 30 cm to give a shock to thecan bottom. Thereafter, the lid was opened, and 1% salt water was pouredin the can so that a portion that had suffered shock was immersed. Afterimmersion for five minutes, a load of 6 V was applied across a platinumelectrode immersed in the liquid and a can metal portion, and thecurrent value after five minutes was read, by which evaluation was madeas described below. The same tests were conducted at room temperature of20° C. and at a temperature of 0° C. The former test was for evaluatingroom-temperature impact resistance, and the latter test was forevaluating low-temperature impact resistance. Grades not lower than ◯marked grade are acceptable.

(Evaluation of Room-temperature Impact Resistance)

Test Result: Grade

-   Current value not lower than 3 mA: (Inferior)-   Current value not lower than 1 mA and lower than 3 mA-   Current value not lower than 0.5 mA and lower than 1 mA-   Current value not lower than 0.1 mA and lower than 0.5 mA-   Current value lower than 0.1 mA: (Superior)    (Evaluation of Low-temperature Impact Resistance)    Test Result: Grade-   Current value not lower than 5 mA: (Inferior)-   Current value not lower than 3 mA and lower than 5 mA-   Current value not lower than 1 mA and lower than 3 mA-   Current value not lower than 0.5 mA and lower than 1 mA-   Current value not lower than 0.1 mA and lower than 0.5 mA-   Current value lower than 0.1 mA: (Superior)    (3) Adhesion After Forming

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was immersed in aqueous solutioncontaining 1.5 wt % citric acid and 1.5 wt % sodium chloride for 24hours. Thereafter, the peeling length of resin in the can end portionwas observed, and evaluation was made as described below. Grades notlower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling length longer than 5 mm: (Inferior).-   Peeling length longer than 2 mm and not longer than 5 mm-   Peeling length longer than 1 mm and not longer than 2 mm-   Peeling length not longer than 1 mm-   No peeling: (Superior)    (4) Adhesion After Heating

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was heated without content therein at210° C. for 10 minutes in an oven. Thereafter, the degree of peeling ofresin in the can end portion was observed, and evaluation was made asdescribed below. Grades not lower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling percentage-higher than 5%: (Inferior)-   Peeling percentage higher than 2% and not higher than 5%-   Peeling percentage higher than 1% and not higher than 2%-   Peeling percentage not higher than 1%.-   No peeling: (Superior)    (5) Flavor Property

The internal surface of can body subjected to straightening heattreatment was cleaned, and flavor aqueous solution (d-limonene 20 ppmaqueous solution) was put in the can and left at ordinary temperaturefor 20 days after sealing. Thereafter, the can was unsealed, and aportion expelled by ether immersion was determined by gas chromatographyas adsorption of d-limonene per can, by which flavor property wasevaluated. Grades not lower than ◯ marked grade are acceptable.

Test Result: Grade

-   Adsorption larger than 200 μg/can: (Inferior)-   Adsorption larger than 100 μg/can and not larger than 200 μg/can-   Adsorption larger than 30 μg/can and not larger than 100 μg/can-   Adsorption larger than 10 μg/can and not larger than 30 μg/can-   Adsorption not larger than 10 μg/can: (Superior)    2. Evaluation by Drawing and Ironing (Di Forming)    2-1 Can Manufacturing

A resin laminated metal sheet was drawn and ironed under the followingconditions, by which a DI can was obtained.

-   First-stage drawing    -   Blank diameter: 150 mm    -   Drawing ratio: 1.6-   Second-stage drawing    -   Drawing ratio: 1.25-   Ironing    -   Ironing punch diameter: 3-stage ironing 65.8 mm dia-   Total ironing percentage of can sidewall    -   60 to 75% with respect to thickness of resin laminated metal        sheet before forming        2-2 Straightening Heat Treatment

Forming strain of film caused by can manufacturing was removed bykeeping the can in a thermal environment of film melting point minus 15°C. for 30 seconds and then by rapidly cooling it.

(1) Formability

Evaluation was made as described below by the limit of capability formanufacturing can without film failure. Grades not lower than ◯ markedgrade are acceptable.

Limit of forming (total ironing percentage): Grade

-   Incapable of forming at total ironing percentage of 60%: (Inferior)-   Capable of forming up to total ironing percentage of 60%-   Capable of forming up to total ironing percentage of 65%-   Capable of forming up to total ironing percentage of 70%-   Capable of forming up to total ironing percentage of 75%: (Superior)    (2) Evaluation of Room-temperature and Low-temperature Impact    Resistance

A can body (total ironing percentage: 70%) subjected to straighteningheat treatment was necked, and the can body was filled with distilledwater. After a lid was installed and tightened, an iron ball of 0.5 kgwas dropped from a height of 25 cm to give a shock to the can bottom.Thereafter, the lid was opened, and 1% salt water was poured in the canso that a portion that had suffered shock was immersed. After immersionfor five minutes, a load of 6 V was applied across a platinum electrodeimmersed in the liquid and a can metal portion, and the current valueafter five minutes was read, by which evaluation was made as describedbelow. The same tests were conducted at room temperature of 20° C. andat a temperature of 0° C. The former test was for evaluatingroom-temperature impact resistance, and the latter test was forevaluating low-temperature impact resistance. Grades not lower than ◯marked grade are acceptable.

(Evaluation of Room-temperature Impact Resistance)

Test Result: Grade

-   Current value not lower than 3 mA: (Inferior)-   Current value not lower than 1 mA and lower than 3 mA-   Current value not lower than 0.5 mA and lower than 1 mA-   Current value not lower than 0.1 mA and lower than 0.5 mA-   Current value lower than 0.1 mA: (Superior)    (Evaluation of Low-Temperature Impact Resistance)    Test Result: Grade-   Current value not lower than 5 mA: (Inferior)-   Current value not lower than 3 mA and lower than 5 mA-   Current value not lower than 1 mA and lower than 3 mA-   Current value not lower than 0.5 mA and lower than 1 mA-   Current value not lower than 0.1 mA and lower than 0.5 mA-   Current value lower than 0.1 mA: (Superior)    (3) Adhesion After Forming

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was immersed in aqueous solutioncontaining 1.5 wt % citric acid and 1.5 wt % sodium chloride for fivehours. Thereafter, the peeling length of resin in the can end portionwas observed, and evaluation was made as described below. Grades notlower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling length longer than 5 mm: (Inferior)-   Peeling length longer than 2 mm and not longer than 5 mm-   Peeling length longer than 1 mm and not longer than 2 mm-   Peeling length not longer than 1 mm-   No peeling: (Superior)    (4) Adhesion After Heating

The internal surface of can body subjected to straightening heattreatment was cleaned, and the can was heated without content therein at210° C. for 10 minutes in an oven. Thereafter, the degree of peeling ofresin in the can end portion was observed, and evaluation was made asdescribed below. Grades not lower than ◯ marked grade are acceptable.

Test Result: Grade

-   Peeling percentage higher than 5%: (Inferior)-   Peeling percentage higher than 2% and not higher than 5%-   Peeling percentage higher than 1% and not higher than 2%-   Peeling percentage not higher than 1%-   No peeling: (Superior)    (5) Flavor Property

The internal surface of can body subjected to straightening heattreatment was cleaned, and flavor aqueous solution (d-limonene 20 ppmaqueous solution) was put in the can and left at ordinary temperaturefor 20 days after sealing. Thereafter, the can was unsealed, and aportion expelled by ether immersion was determined by gas chromatographyas adsorption of d-limonene per can, by which flavor property wasevaluated. Grades not lower than ◯ marked grade are acceptable.

Test Result: Grade

-   Adsorption larger than 200 μg/can: (Inferior)-   Adsorption larger than 100 μg/can and not larger than 200 μg/can-   Adsorption larger than 30 μg/can and not larger than 100 μg/can-   Adsorption larger than 10 μg/can and not larger than 30 μg/can-   Adsorption not larger than 10 μg/can: (Superior)

The investigation results are given in Tables 30 and 31.

From Tables 27 to 31, the following facts are found for either can type.

Invention examples 1 to 4 are films in which R1 layer is a mixed resinlayer in which modified polyolefin resin specified in the presentinvention is dispersed in various types of polyester resins and amodified polyolefin resin layer specified in the present invention isalso used in R2 layer, and invention examples 47 to 50 in which thesefilms are laminated on the metal sheet of the present invention exhibithigh formability, impact resistance, adhesion, and flavor property.Among these, invention example 49 using adipic acid copolymerizedpolyethylene terephthalate resin has high performance as a whole, buthas a tendency toward low adhesion after heating and flavor propertybecause of slightly low melting point of polyester resin and slightlylow barrier property. Also, invention example 87 in which the film ofinvention example 41 manufactured from a commercially available resin inwhich modified polyolefin resin is dispersed in polyester resinsimilarly exhibits high performance. On the other hand, comparativeexamples 1 to 5 are examples of films in which modified polyolefin resinspecified in the present invention is not contained in polyester resinin which polyester type is changed variously. Comparative examples 20 to24 in which these films are laminated especially have low levels offormability and impact resistance.

Invention examples 4 to 10 are films using a mixed resin in whichvarious types of modified polyolefin resins specified in the presentinvention are dispersed in polyester resin, and invention examples 50 to56 in which the films are laminated exhibit high formability, impactresistance, adhesion, and flavor property. In particular, inventionexamples 50 and 52 to 54 in which the films of invention examples 4 and6 to 8 using modified polyolefin resin containing a proper amount offunctional group derived from carboxylic acid and having aglass-transition temperature of −30° C. or lower are laminated haveexcellent formability, impact resistance, adhesion, and flavor property.On the other hand, comparative example 6 is a film using, as R1 layer, amixed resin in which polyolefin resin containing no functional groupderived from carboxylic acid is dispersed in polyester resin, andcomparative example 25 in which the film is laminated has greatlydeteriorated formability and impact resistance.

Invention examples 11 to 18 are films in which the blending ratio anddispersion state of modified polyolefin resin dispersed in polyesterresin of R1 mixed resin layer are changed variously in the range of thepresent invention, and invention examples 57 to 64 in which the filmsare laminated on a metal sheet exhibit high formability, impactresistance, adhesion, and flavor property. In particular, inventionexamples 58, 60 and 61 in which the films of invention examples 12, 14and 15 containing a proper amount of dispersed modified polyolefin resinand having a proper number of grains per a fixed volume are laminatedhave excellent formability, impact resistance, adhesion, and flavorproperty.

On the other hand, comparative examples 7 to 10 are films in which theblending ratio of modified polyolefin resin in polyester resin of R1mixed resin layer does not meet the requirement of the presentinvention, and comparative examples 26 to 29 in which the films arelaminated have greatly deteriorated formability or impact resistance.Comparative example 26 in which the film of comparative example 7 havinga small number of grains of dispersed modified polyolefin resin islaminated and comparative example 29 in which the film of comparativeexample 10 having a large number of grains of modified polyolefin resinis laminated have greatly deteriorated formability and impactresistance.

Invention examples 19 to 25 are films in which the thickness of R1 layerand R2 layer of film is changed in the range specified in the presentinvention, and invention examples 65 to 71 in which the films arelaminated on a metal sheet exhibit high formability, impact resistance,adhesion, and flavor property. Among these, invention examples 66, 67and 69 in which the films of invention examples 20, 21 and 23 in whichthe thickness ratio of R1 layer to R2 layer is in the range of 5 to 10and the thickness of R1 layer is in the range of 15 to 25 μm arelaminated have excellent formability, impact resistance, adhesion, andflavor property. Also, invention example 13a is a film in which thethickness ratio R1/R2 of mixed resin layer of R1 to modified polyolefinlayer of R2 is lower than the desired range of the present invention,and invention example 32a in which this film is laminated has slightlydeteriorated mechanical properties of film and adhesion to a substratemetal sheet as compared with invention examples 65 to 71. On the otherhand, invention example 14a is a film in which the ratio R1/R2 is higherthan the proper range of the present invention, and invention example33a in which this film is laminated has slightly deteriorated adhesionto a substrate metal sheet as compared with invention examples 65 to 71.

Invention examples 26 to 31 are films using various types of modifiedpolyolefin resins specified in the present invention as R2 layer, andinvention examples 72 to 77 in which the films are laminated exhibithigh formability, impact-resistance, adhesion, and flavor property. Inparticular, invention examples 73 to 75 in which the films of inventionexamples 27 to 29 using modified polyolefin resin containing a properamount of functional group derived from carboxylic acid and having aglass-transition temperature of −30° C. or lower are laminated haveexcellent formability, impact resistance, adhesion, and flavor property.On the other hand, comparative example 13 is a film using, as R2 layer,polyolefin resin containing no functional group derived from carboxylicacid, and comparative example 32 in which the film is laminated hasgreatly deteriorated formability and impact resistance.

Invention examples 32 to 34 are films in which a lubricant, free radicalinhibitor, and compatibilizing agent are mixed, respectively, in a mixedresin of modified polyolefin resin and polyester resin of the presentinvention, and invention examples 78 to 80 in which the films arelaminated exhibit high formability, impact resistance, adhesion, andflavor property. Further, invention examples 78 to 80 also havelubricity, free radical deterioration resistance, and compatibilitydepending on the function of added additive, and in particular,invention example 80 containing a compatibilizing agent exhibitsexcellent low-temperature impact resistance.

Invention example 35 is a film of the present invention that ismanufactured by the two-axis stretching method, and invention examples81 and 97 in which the film is laminated exhibit high performance.Invention example 97, which has a plane orientation coefficient of0.015, exhibits a slightly deteriorated formability. However, inventionexample 81, which has a plane orientation coefficient in the range ofthe present invention, has a high level of impact-resistance.

Invention examples 36 to 40 are films in which titanium dioxide pigmentis mixed with the film of the present invention, and invention examples82 to 86 in which the films are laminated exhibit high formability,impact resistance, adhesion, and flavor property, and also provide awhite uniform color tone. However, invention example 82 in which thefilm of invention example 36 in which the added amount of pigment issmaller than a desired range is laminated has slightly insufficientopacifying property of color tone. On the other hand, invention example86 in which the film of invention example 40 in which the added amountof pigment is larger than a desired range is laminated has slightlydeteriorated formability.

Invention examples 93 to 96 are films obtained by changing thelaminating conditions for the film of invention example 4 in the rangeof the present invention. If the conditions are within the range of thepresent invention, high formability, impact resistance, adhesion, andflavor property are exhibited regardless of the laminating temperature.

Invention examples 42 to 46 are three-layer films in which a polyesterresin layer of R0 layer containing no olefin and a mixed resin layer ofR1 layer and a modified polyolefin layer of R2 layer are laminated (R0layer is laminated on R1 layer), and invention examples 88 to 92 inwhich the three-layer films are laminated have very high formability,impact resistance, adhesion, and flavor property. In particular,invention examples 88, 89 and 92 in which the films using, as R0 layer,a polyester resin layer with a proper thickness that consists ofpolyethylene terephthalate or isophthalic acid copolymerizedpolyethylene terephthalate are laminated have excellent low-temperatureimpact resistance and flavor property.

Invention examples 15a and 16a are three-layer films in which apolyester resin layer of R0 layer containing no olefin and a mixed resinlayer of R1 layer and a modified polyolefin layer of R2 layer arelaminated (R0 layer is laminated on R1 layer) but R2 layer deviates fromthe proper range of the present invention, and invention examples 34aand 35a in which the three-layer films are laminated have deterioratedadhesion as compared with invention examples 42 to 46 in which R2 layeris within the proper range of the present invention.

TABLE 27 R1 layer Polyolefin resin Number of grains R2 layer Volume withPolyolefin resin Entire film Weight percentage diameter Weight Thicknesspercentage of grains of 0.1 to percentage ratio R0 layer of groupBlending with 5 μm in of group of R1 Film Polyester derived ratio indiameter cube with Film derived Film layer Pigment Polyester thick-resin from entire of 0.1 to one side thick- from Film thickness to R0Content Sample resin ness Resin Resin carboxylic Tg resin 5 μm of 10 μmness Resin carboxylic Tg thickness (R1 + R0) layer (wt %) film type (μm)type Additive type acid (wt %) (° C.) (wt %) (vol %) (grains) (μm) typeacid (wt %) (° C.) (μm) (μm) R1/R0 Type *1) Stretching Inventive PETNone EM4 8 <−30 15 12 2000 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 1stretched Inventive PET/ None EM4 8 <−30 15 12 2000 22 EM6 5 <−30 4 265.5 None 0 Non- example 2 PBT stretched Inventive PET/ None EM4 8 <−3015 12 2000 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 3 AD stretchedInventive PET/I None EM4 8 <−30 15 12 2000 22 EM6 5 <−30 4 26 5.5 None 0Non- example 4 stretched Inventive PET/I None EM1 21 <−30 15 14 40 22EM6 5 <−30 4 26 5.5 None 0 Non- example 5 stretched Inventive PET/I NoneEM2 18 <−30 15 13 500 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 6stretched Inventive PET/I None EM5 7 <−30 15 12 2000 22 EM6 5 <−30 4 265.5 None 0 Non- example 7 stretched Inventive PET/I None EM6 5 <−30 1512 2000 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 8 stretched InventivePET/I None EM7 1 <−30 15 3 20 22 EM6 5 <−30 4 26 5.5 None 0 Non- example9 stretched Inventive PET/I None EM8 6 20 15 12 2000 22 EM6 5 <−30 4 265.5 None 0 Non- example 10 stretched Inventive PET/I None EM3 11 <−30 53 3 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 11 stretched InventivePET/I None EM3 11 <−30 5 5 70 22 EM6 5 <−30 4 26 5.5 None 0 Non- example12 stretched Inventive PET/I None EM3 11 <−30 10 8 30 22 EM6 5 <−30 4 265.5 None 0 Non- example 13 stretched Inventive PET/I None EM3 11 <−30 1010 250 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 14 stretched InventivePET/I None EM3 11 <−30 15 15 500 22 EM6 5 <−30 4 26 5.5 None 0 Non-example 15 stretched Inventive PET/I None EM3 11 <−30 15 18 20000 22 EM65 <−30 4 26 5.5 None 0 Non- example 16 stretched Inventive PET/I NoneEM3 11 <−30 20 22 200000 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 17stretched Inventive PET/I None EM3 11 <−30 28 20 8000 22 EM6 5 <−30 4 265.5 None 0 Non- example 18 stretched Inventive PET/I None EM6 5 <−30 1512 2000 10 EM6 5 <−30 1 11 10.0 None 0 Non- example 19 stretchedInventive PET/I None EM6 5 <−30 15 12 2000 15 EM6 5 <−30 3 18 5.0 None 0Non- example 20 stretched Inventive PET/I None EM6 5 <−30 15 12 2000 20EM6 5 <−30 3 23 6.7 None 0 Non- example 21 stretched Inventive PET/INone EM6 5 <−30 15 12 2000 20 EM6 5 <−30 10 30 2.0 None 0 Non- example22 stretched Inventive PET/I None EM6 5 <−30 15 12 2000 25 EM6 5 <−30 328 8.3 None 0 Non- example 23 stretched Inventive PET/I None EM6 5 <−3015 12 2000 35 EM6 5 <−30 5 40 7.0 None 0 Non- example 24 stretchedInventive PET/I None EM6 5 <−30 15 12 2000 40 EM6 5 <−30 6 46 6.7 None 0Non- example 25 stretched *1) Pigment content means weight percentage(wt %) of pigment with respect to total film amount of entire resin andpigment: Pigment is added to R1 layer.

TABLE 28 R1 layer Polyolefin resin Number of grains R2 layer Volume withPolyolefin resin Entire film Weight percentage diameter Weight Thicknesspercentage of grains of 0.1 to percentage ratio R0 layer of groupBlending with 5 μm in of group of R1 Film Polyester derived ratio indiameter cube with Film derived Film layer Pigment Polyester thick-resin from entire of 0.1 to one side thick- from Film thickness to R0Content Sample resin ness Resin Resin carboxylic Tg resin 5 μm of 10 μmness Resin carboxylic Tg thickness (R1 + R0) layer (wt %) film type (μm)type Additive type acid (wt %) (° C.) (wt %) (vol %) (grains) (μm) typeacid (wt %) (° C.) (μm) (μm) R1/R0 Type *1) Stretching Inventive PET/INone EM6 5 <−30 15 12 2000 22 EM1 21 <−30 4 26 5.5 None 0 Non- example26 stretched Inventive PET/I None EM6 5 <−30 15 12 2000 22 EM2 18 <−30 426 5.5 None 0 Non- example 27 stretched Inventive PET/I None EM6 5 <−3015 12 2000 22 EM4 8 <−30 4 26 5.5 None 0 Non- example 28 stretchedInventive PET/I None EM6 5 <−30 15 12 2000 22 EM5 7 <−30 4 26 5.5 None 0Non- example 29 stretched Inventive PET/I None EM6 5 <−30 15 12 2000 22EM7 1 <−30 4 26 5.5 None 0 Non- example 30 stretched Inventive PET/INone EM6 5 <−30 15 12 2000 22 EM8 6 20 4 26 5.5 None 0 Non- example 31stretched Inventive PET/I *2) EM3 11 <−30 15 12 2000 22 EM6 5 <−30 4 265.5 None 0 Non- example 32 0.3 wt % stretched Inventive PET/I *3) EM3 11<−30 15 12 2000 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 33 0.1 wt %stretched Inventive PET/I *4) EM3 11 <−30 15 12 2000 22 EM6 5 <−30 4 265.5 None 0 non- example 34   3 wt % stretched Inventive PET/I None EM4 8<−30 15 12 2000 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 35 stretchedInventive PET/I None EM5 7 <−30 15 12 2000 22 EM6 5 <−30 4 26 5.5 TIO₂ 3Two-axis example 36 stretched Inventive PET/I None EM5 7 <−30 15 12 200022 EM6 5 <−30 4 26 5.5 TiO₂ 7 Non- example 37 stretched Inventive PET/INone EM5 7 <−30 15 12 2000 22 EM6 5 <−30 4 26 5.5 TiO₂ 15 Non- example38 stretched Inventive PET/I None EM5 7 <−30 15 12 2000 22 EM6 5 <−30 426 5.5 TiO₂ 30 Non- example 39 stretched Inventive PET/I None EM5 7 <−3015 12 2000 22 EM6 5 <−30 4 26 5.5 TiO₂ 50 Non- example 40 stretchedInventive PET None 15 <−30 15 15 2500 25 EM6 5 <−30 3 28 8.3 None 0 Non-example 41 (PT stretched 4274) Inventive PET 8 PET/I None EM6 5 <−30 1512 2000 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 42 stretchedInventive PET/I 4 PET/I None EM6 5 <−30 15 12 2000 22 EM6 5 <−30 4 265.5 None 0 Non- example 43 stretched Inventive PET/ 4 PET/I None EM6 5<−30 15 12 2000 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 44 PBTstretched Inventive PET/ 4 PET/I None EM6 5 <−30 15 12 2000 22 EM6 5<−30 4 26 5.5 None 0 Non- example 45 AD stretched Inventive PET 4 PETNone 15 <−30 15 15 2500 25 EM6 5 <−30 3 28 8.3 None 0 Non example 46 (PTstretched 4274) *1) Pigment Content means weight percentage (wt %) ofpigment with respect to total film amount of entire resin and pigment.Pigment is added to R1 layer. *2) Silicone of lubricant is added by 3weight part to 100 weight part of mixed resin. *3) Tetrakis-[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane of free radicalinhibitor is added by 0.1 weight part to 100 weight part of mixed resin.*4) Bond first 20B (manufactured by Sumitomo Chemical Co., Ltd.) ofcompatibilizing agent is added by 3 weight part to 100 weight part ofmixed resin.

TABLE 29 R1 layer Polyolefin resin Number of grains R2 layer Volume withPolyolefin resin Entire film Weight percentage diameter Weight Thicknesspercentage of grains of 0.1 to percentage ratio R0 layer of groupBlending with 5 μm in of group of R1 Film Polyester derived ratio indiameter cube with Film derived Film layer Pigment Polyester thick-resin from entire of 0.1 to one side thick- from Film thickness to R0Content Sample resin ness Resin Resin carboxylic Tg resin 5 μm of 10 μmness Resin carboxylic Tg thickness (R1 + R0) layer (wt %) film type (μm)type Additive type acid (wt %) (° C.) (wt %) (vol %) (grains) (μm) typeacid (wt %) (° C.) (μm) (μm) R1/R0 Type *1) Stretching Comparative PETNone None — — 0 0 0 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 1stretched Comparative PET/ None None — — 0 0 0 22 EM6 5 <−30 4 26 5.5None 0 Non- example 2 PBT stretched Comparative PET/ None None — — 0 0 022 EM6 5 <−30 4 26 5.5 None 0 Non- example 3 AD stretched ComparativePET/I None None — — 0 0 0 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 4stretched Comparative PET/I None None — — 0 0 0 22 EM6 5 <−30 4 26 5.5None 0 Two-axis example 5 stretched Comparative PET/I None EPR 0 <−30 151 5 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 6 stretched ComparativePET/I None EM3 11 <−30 2 2 3 22 EM6 5 <−30 4 26 5.5 None 0 Non- example7 stretched Comparative PET/I None EM3 11 <−30 2 2 45 22 EM6 5 <−30 4 265.5 None 0 Non- example 8 stretched Comparative PET/I None EM3 11 <−3032 28 15000 22 EM6 5 <−30 4 26 5.5 None 0 Non- example 9 stretchedComparative PET/I None EM3 11 <−30 32 28 120000 22 EM6 5 <−30 4 26 5.5None 0 Non- example 10 stretched Comparative PET/I None EM4 8 <−30 15 122000 22 None — — — — — None 0 Non- example 11 stretched Comparative PETNone 15 <−30 15 15 2500 25 None — — — — — None 0 Non- example 12 (PTstretched 4274) Inventive PET/I None EM4 8 <−30 15 12 2000 10 EM6 5 <−3012  22 0.8 None 0 Non- example 13a stretched Inventive PET/I None EM4 8<−30 15 12 2000 32 EM6 5 <−30 3 35 10.7  None 0 Non- example 14astretched Inventive PET/I None EM4 8 <−30 15 12 2000 22 EPR 0 <−30 4 265.5 None 0 Non- example 13 stretched Inventive PET 4 PET/I None EM4 8<−30 15 12 2000 22 None — — — — — None 0 Non- example 14 stretchedComparative PET 4 PET None 15 <−30 15 15 2500 25 None — — — — — None 0Non- example 15 (PT stretched 4274) Inventive PET 4 PET/I None EM4 8<−30 15 12 2000 10 EM6 5 <−30 12  22 0.8 None 0 Non- example 15astretched Inventive PET 4 PET/I None EM4 8 <−30 15 12 2000 32 EM6 5 <−303 35 10.7  None 0 Non- example 16a stretched *1) Pigment content meansweight percentage (wt %) of pigment with respect to total film amount ofentire resin and pigment. Pigment is added to R1 layer

TABLE 30 Melting Thin-wall deep drawn can Drawn and ironed can (DI can)point Impact Impact Laminated of R1 layer Laminating Plane Impactresistance Adhesion Adhesion Impact resistance Adhesion Adhesion metalSample polyester temp. orientation resistance (low after after Flavorresistance (low after after Flavor sheet film resin (° C.) (° C.)coefficient Formability (room temp.) temp.) forming heating propertyFormability (room temp.) temp.) forming heating property InventionInvention 255 235 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 47 example 1Invention Invention 235 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 48example 2 Invention Invention 220 210 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 49 example 3 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 50 example 4 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 51 example 5 Invention Invention 230 220 0⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 52 example 6 Invention Invention230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 53 example 7 InventionInvention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 54 example 8Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 55example 9 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 56 example 10 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 57 example 11 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 58 example 12 Invention Invention 230220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 59 example 13 InventionInvention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 60 example14 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example61 example 15 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 62 example 16 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 63 example 17 Invention Invention 230 220 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 64 example 18 Invention Invention230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 65 example 19Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 66example 20 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 67 example 21 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 68 example 22 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 69 example 23 Invention Invention 230220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 70 example 24 InventionInvention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 71 example25 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example72 example 26 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 73 example 27 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 74 example 28 Invention Invention 230 220 0 ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 75 example 29 Invention Invention230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 76 example 30Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 77example 31 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 78 example 32 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 79 example 33 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 80 example 34 Invention Invention 230220 0.005 ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 81 example 35

TABLE 31 Melting point Thin-wall deep drawn can Laminated of R1 layerLaminating Plane Impact Impact Adhesion metal Sample polyester temp.orientation resistance resistance after sheet film resin (° C.) (° C.)coefficient Formability (room temp.) (low temp.) forming InventionInvention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 82 example 36 Invention Invention230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 83 example 37 Invention Invention 230 220 0⊚ ⊚ ⊚⊚⊚ ⊚ example 84 example 38 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 85 example 39 Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 86example 40 Invention Invention 255 235 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 87 example 41Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 88 example 42 InventionInvention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 89 example 43 Invention Invention230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 90 example 44 Invention Invention 230 220 0⊚ ⊚ ⊚⊚⊚ ⊚ example 91 example 45 Invention Invention 255 235 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 92 example 46 Invention Invention 230 260 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 93example 4 Invention Invention 230 240 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 94 example 4Invention Invention 230 200 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 95 example 4 InventionInvention 230 170 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 96 example 4 Invention Invention235 200 0.015 ⊚ ⊚ ⊚⊚⊚ ⊚ example 97 example 35 Comparative Comparative255 235 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 20 example 1 Comparative Comparative 235 2200 ⊚ ⊚ ⊚⊚⊚ ⊚ example 21 example 2 Comparative Comparative 220 210 0 ⊚ ⊚⊚⊚⊚ ⊚ example 22 example 3 Comparative Comparative 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 23 example 4 Comparative Comparative 230 220 0.005 ⊚ ⊚ ⊚⊚⊚ ⊚example 24 example 5 Comparative Comparative 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example25 example 6 Comparative Comparative 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 26example 7 Comparative Comparative 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 27 example8 Comparative Comparative 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 28 example 9Comparative Comparative 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 29 example 10Comparative Comparative 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 30 example 11Comparative Comparative 255 235 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 31 example 12Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 32a example 13aInvention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 33a example 14aComparative Comparative 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 32 example 13Comparative Comparative 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 33 example 14Comparative Comparative 255 235 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 34 example 15Invention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 34a example 15aInvention Invention 230 220 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 35a example 16aThin-wall deep drawn can Drawn and ironed can (DI can) LaminatedAdhesion Impact Impact Adhesion Adhesion metal after Flavor resistanceresistance after after Flavor sheet heating property Formability (roomtemp.) (low temp.) forming heating Property Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 82 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 83 Invention ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 84 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 85Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 86 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 87 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 88 Invention ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 89 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 90Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 91 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 92 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 93 Invention ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 94 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 95Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 96 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 97 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 20 Comparative⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 21 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 22 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 23 Comparative ⊚⊚⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 24 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example25 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 26 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 27 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 28Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 29 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ example 30 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 31 Invention⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 32a Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 33a Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 32 Comparative ⊚⊚⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 33 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example34 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 34a Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ example 35a

Example 8

As a resin raw material for R1 layer, modified polyolefin resin withgroup derived from carboxylic acid was cold blended with polyester resinin a blending ratio given in Tables 32 to 34 by using a tumbler blender,and then the blended resin was melted and kneaded at 270° C. by using atwo-axis extruding machine, by which a raw material pellet of polyesterresin in which modified polyolefin resin was dispersed was obtained. Inthe tables, the resin type corresponding to the symbol of resin type ofpolyester resin and resin type of polyolefin resin is the same as thatdescribed in Example 7. As some resin raw material for R1 layer, acommercially available resin (Sealer PT4274 manufactured byMitsui-DuPont Polychemical Co., Ltd.) that had been pelletized inadvance in a state in which modified polyolefin resin with group derivedfrom carboxylic acid was dispersed in polyester resin was used as itwas.

As a metal sheet, as in Example 7, a TFS with a thickness of 0.18 mm forthin-wall deep drawn can and 0.23 mm for DI can, which had a degree oftemper of DR9, metallic chromium layer of 80 mg/m², and chromium oxidelayer of 15 mg/m² (metallic chromium conversion), was used, by which aboth-side laminated metal sheet was obtained by a method in which theraw material resin pellet for R1 layer was inserted in a one-axisextruding machine, modified polyolefin, which was a resin raw materialfor R2 layer, was inserted in a separate extruding machine in the caseof two layers, each of molten resins was introduced into amulti-manifold type T die and extruded in two layers while the filmthickness of R1 and R2 layers was controlled by the discharge amount ofmolten resin from the extruding machine, molten resin was directlyextruded onto one surface of the metal sheet heated to 230° C. inadvance, the extruded resin was once cooled while being held adherentlybetween two rolls, and immediately after the resin was laminated on theopposite surface in the same manner, the resin laminated metal sheet wascooled rapidly in water.

Also, in the case of three-layer construction having R0 layer, aboth-side laminated metal sheet was obtained by a method in whichpolyester resin, which was a resin raw material for R0 layer, wasinserted in a separate one-axis extruding machine, each of molten resinswas introduced into a multi-manifold type T die and extruded in threelayers while the film thickness of R0, R1 and R2 layers was controlledby the discharge amount of molten resin from the extruding machine,molten resin was directly extruded onto one surface of the metal sheetheated to 230° C. in advance, the extruded resin was once cooled whilebeing held adherently between two rolls, and immediately after the resinwas laminated on the opposite surface in the same manner, the resinlaminated metal sheet was cooled rapidly in water. The lip opening widthof T die was adjusted so that the thickness of resin film was as givenin Tables 32 to 34. The type of sample resin and the resin meltingtemperature at the extrusion laminating time are given in Tables 32 and37. The used polyester resin and modified polyolefin resin with groupderived from carboxylic acid are the same as those used in Example 7.

All of the grain diameter of modified polyolefin resin dispersed inresin film, various temperatures in the table, and the method formeasuring the plane orientation coefficient of resin laminated metalsheet are the same as those in Example 7. As in Example 7, a thin-walldeep drawn can or a DI can was manufactured from the laminated metalsheet obtained as described above, and the can was subjected tostraightening heat treatment to manufacture a sample can. Theformability, impact resistance, adhesion, and flavor property of film ofthe manufactured can body were investigated as in Example 7.

The investigation results are given in Tables 35 and 37.

From Tables 32 to 37, the following facts are found for either can type.

Invention examples 98 to 101 are resin laminated steel sheets in whichR1 layer is a mixed resin layer in which modified polyolefin resinspecified in the present invention is dispersed in various types ofpolyester resins and a modified polyolefin resin layer specified in thepresent invention is also used in R2 layer, and exhibit highformability, impact resistance, adhesion, and flavor property. Amongthese, invention example 100 using adipic acid copolymerizedpolyethylene terephthalate resin has high performance as a whole, buthas a tendency toward low adhesion after heating and flavor propertybecause of slightly low melting point of polyester resin and slightlylow barrier property. Also, invention example 137 of resin laminatedsteel sheet manufactured from a commercially available resin in whichmodified polyolefin resin is dispersed in polyester resin similarlyexhibits high performance. On the other hand, comparative examples 39 to42 are examples of resin laminated steel sheets in which modifiedpolyolefin resin specified in the present invention is not contained inpolyester resin in which polyester type is changed variously, andespecially have low levels of formability and impact resistance.

Invention examples 101 to 107 are examples of resin laminated steelsheets using a mixed resin in which various types of modified polyolefinresins specified in the present invention are dispersed in polyesterresin, and exhibit high formability, impact resistance, adhesion, andflavor property. In particular, invention examples 101 and 103 to 105using modified polyolefin resin containing a proper amount of functionalgroup derived from carboxylic acid and having a glass-transitiontemperature of −30° C. or lower have excellent formability, impactresistance, and adhesion. On the other hand, comparative example 43 isan example using, as R1 layer, a mixed resin in which polyolefin resincontaining no functional group derived from carboxylic acid is dispersedin polyester resin, and has greatly deteriorated formability and impactresistance.

Invention examples 108 to 115 are resin laminated steel sheets in whichthe blending ratio and dispersion state of modified polyolefin resindispersed in polyester resin of R1 mixed resin layer are changedvariously in the range of the present invention, and exhibit highformability, impact resistance, and adhesion. In particular, inventionexamples 109, 111 and 112 containing a proper amount of dispersedmodified polyolefin resin and having a proper number of grains per afixed volume have excellent formability, impact resistance, adhesion,and flavor property.

On the other hand, comparative examples 44 to 47 are examples in whichthe blending ratio of modified polyolefin resin in polyester resin of R1mixed resin layer does not meet the requirement of the presentinvention, and have greatly deteriorated formability or impactresistance. Comparative example 44 containing a small amount ofdispersed modified polyolefin resin and comparative example 47containing a large amount of modified polyolefin resin have greatlydeteriorated formability and impact resistance.

Invention examples 116 to 122 are examples in which the thickness of R1layer and R2 layer is changed in the range specified in the presentinvention, and exhibit high formability, impact resistance, adhesion,and flavor property. Among these, invention examples 117, 118 and 120 inwhich the thickness ratio R1/R2 of R1 layer to R2 layer is in the rangeof 5 to 10 and the thickness of R1 layer is in the range of 15 to 25 μmhave excellent formability, impact resistance, adhesion, and flavorproperty. Also, invention example 143 is an example in which thethickness ratio R1/R2 of R1 layer to R2 layer is lower than the properrange of the present invention, and has slightly deteriorated mechanicalproperties of resin and adhesion to a substrate metal sheet as comparedwith invention examples 116 to 122. On the other hand, invention example144 is an example in which the ratio R1/R2 is higher than the properrange of the present invention, and has slightly deteriorated adhesionto a substrate metal sheet as compared with invention examples 116 to122.

Invention examples 123 to 128 are resin laminated steel sheets usingvarious types of modified polyolefin resins specified in the presentinvention as R2 layer, and exhibit high formability, impact resistance,adhesion, and flavor property. In particular, invention examples 124 to126 using modified polyolefin resin containing a proper amount offunctional group derived from carboxylic acid and having aglass-transition temperature of −30° C. or lower have excellentformability, impact resistance, adhesion, and flavor property.

Invention examples 129 to 131 are resin laminated steel sheets in whicha lubricant, free radical inhibitor, and compatibilizing agent aremixed, respectively, in a mixed resin of modified polyolefin resin andpolyester resin of the present invention, and exhibit high formability,impact resistance, adhesion, and flavor property. Further, inventionexamples 129 to 131 also have lubricity, free radical deteriorationresistance, and compatibility depending on the function of addedadditive, and in particular, invention example 131 containing acompatibilizing agent exhibits excellent low-temperature impactresistance.

Invention examples 132 to 136 are resin laminated steel sheets in whichtitanium dioxide pigment is mixed with the resin layer of the presentinvention, and exhibit high formability, impact resistance, adhesion,and flavor property, and also provide a white uniform color tone.However, invention example 132 in which the added amount of pigment issmaller than a desired range has slightly insufficient opacifyingproperty of color tone. On the other hand, invention example 136 inwhich the added amount of pigment is larger than a desired range hasslightly deteriorated formability.

Invention examples 138 to 142 are steel sheets on which three-layerresin in which a polyester resin layer containing no olefin (R0 layer)is further provided on R1 layer is laminated, have very highformability, impact resistance, adhesion, and flavor property. Inparticular, invention examples 138, 139 and 142 using, as R0 layer, apolyester resin layer with a proper thickness that consists ofpolyethylene terephthalate or isophthalic acid copolymerizedpolyethylene terephthalate specified in the present invention haveexcellent low-temperature impact resistance and flavor property.

Invention examples 145 and 146 are steel sheets on which three-layerresin in which a polyester resin layer containing no olefin (R0 layer)is further provided on R1 layer is laminated, and have deterioratedadhesion as compared with invention examples 138 to 142 because thethickness ratio R1/R2 of R1 layer to R2 layer deviates from the properrange of the present invention.

TABLE 32 R1 layer Polyolefin resin Weight R0 layer Polyester percentageResin resin of group Blending Polyester layer Melting derived from ratioin Sample resin thickness Resin point Resin carboxylic Tg entire filmtype (μm) type (° C.) Additive type acid (wt %) (° C.) resin (wt %)Inventive PET 255 None EM4 8 <−30 15 example 98 Inventive PET/ 235 NoneEM4 8 <−30 15 example 99 PBT Inventive PET/ 220 None EM4 8 <−30 15example 100 AD Inventive PET/I 230 None EM4 8 <−30 15 example 101Inventive PET/I 230 None EM1 21 <−30 15 example 102 Inventive PET/I 230None EM2 18 <−30 15 example 103 Inventive PET/I 230 None EM5 7 <−30 15example 104 Inventive PET/I 230 None EM6 5 <−30 15 example 105 InventivePET/I 230 None EM7 1 <−30 15 example 106 Inventive PET/I 230 None EM8 620 15 example 107 Inventive PET/I 230 None EM3 11 <−30 5 example 108Inventive PET/I 230 None EM3 11 <−30 5 example 109 Inventive PET/I 230None EM3 11 <−30 10 example 110 Inventive PET/I 230 None EM3 11 <−30 10example 111 Inventive PET/I 230 None EM3 11 <−30 15 example 112Inventive PET/I 230 None EM3 11 <−30 15 example 113 Inventive PET/I 230None EM3 11 <−30 20 example 114 Inventive PET/I 230 None EM3 11 <−30 28example 115 Inventive PET/I 230 None EM6 5 <−30 15 example 116 InventivePET/I 230 None EM6 5 <−30 15 example 117 Inventive PET/I 230 None EM6 5<−30 15 example 118 Inventive PET/I 230 None EM6 5 <−30 15 example 119Inventive PET/I 230 None EM6 5 <−30 15 example 120 Inventive PET/I 230None EM6 5 <−30 15 example 121 Inventive PET/I 230 None EM6 5 <−30 15example 122 R2 layer R1 layer Polyolefin resin Polyolefin resin WeightNumber of percentage Melting Volume grains with of group temp. ofpercentage diameter of derived R1 layer of grains 0.1 to 5 μm in fromResin resin at with diameter cube with one Film carboxylic layerextrusion Sample of 0.1 to 5 μm side of 10 μm thickness Resin acid Tgthickness laminating film (vol %) (grains) (μm) type (wt %) (° C.) (μm)time (° C.) Inventive 14 2500 22 EM6 21 <−30 4 285 example 98 Inventive14 2500 22 EM6 18 <−30 4 265 example 99 Inventive 14 3000 22 EM6 8 <−304 250 example 100 Inventive 14 2500 22 EM6 7 <−30 4 260 example 101Inventive 16 50 22 EM6 1 <−30 4 260 example 102 Inventive 15 1000 22 EM66 20 4 260 example 103 Inventive 14 2500 22 EM6 5 <−30 4 260 example 104Inventive 14 2500 22 EM6 5 <−30 4 260 example 105 Inventive 4 40 22 EM65 <−30 4 260 example 106 Inventive 14 2500 22 EM6 5 <−30 4 260 example107 Inventive 4 4 22 EM6 5 <−30 4 260 example 108 Inventive 8 100 22 EM65 <−30 4 260 example 109 Inventive 10 50 22 EM6 5 <−30 4 260 example 110Inventive 12 500 22 EM6 5 <−30 4 260 example 111 Inventive 18 800 22 EM65 <−30 4 260 example 112 Inventive 20 22000 22 EM6 5 <−30 4 260 example113 Inventive 24 250000 22 EM6 5 <−30 4 260 example 114 Inventive 2210000 22 EM6 5 <−30 4 260 example 115 Inventive 14 2500 10 EM6 5 <−30 1260 example 116 Inventive 14 2500 15 EM6 5 <−30 3 260 example 117Inventive 14 2500 20 EM6 5 <−30 3 260 example 118 Inventive 14 2500 20EM6 5 <−30 10 260 example 119 Inventive 14 2500 25 EM6 5 <−30 3 260example 120 Inventive 14 2500 35 EM6 5 <−30 5 260 example 121 Inventive14 2500 40 EM6 5 <−30 6 260 example 122

TABLE 33 R1 layer Polyolefin resin Weight R0 layer Polyester percentageResin resin of group Blending Polyester layer Melting derived from ratioin Sample resin thickness Resin point Resin carboxylic Tg entire filmtype (μm) type (° C.) Additive type acid (wt %) (° C.) resin (wt %)Inventive PET 230 None EM6 5 <−30 15 example 123 Inventive PET/I 230None EM6 5 <−30 15 example 124 Inventive PET/I 230 None EM6 5 <−30 15example 125 Inventive PET/I 230 None EM6 5 <−30 15 example 126 InventivePET/I 230 None EM6 5 <−30 15 example 127 Inventive PET/I 230 None EM6 5<−30 15 example 128 Inventive PET/I 230 *2) 0.3 EM3 11 <−30 15 example129 wt % Inventive PET/I 230 *3) 0.1 EM3 11 <−30 15 example 130 wt %Inventive PET/I 230 *4) 3 EM3 11 <−30 15 example 131 wt % InventivePET/I 230 None EM5 7 <−30 15 example 132 Inventive PET/I 230 None EM5 7<−30 15 example 133 Inventive PET/I 230 None EM5 7 <−30 15 example 134Inventive PET/I 230 None EM5 7 <−30 15 example 135 Inventive PET/I 230None EM5 7 <−30 15 example 136 Inventive PET 255 None 15 <−30 15 example137 (PT 4274) Inventive PET 8 PET/I 230 None EM6 5 <−30 15 example 138Inventive PET/I 4 PET/I 230 None EM6 5 <−30 15 example 139 InventivePET/ 4 PET/I 230 None EM6 5 <−30 15 example 140 PBT Inventive PET/ 4PET/I 230 None EM6 5 <−30 15 example 141 AD Inventive PET 4 PET 255 None15 <−30 15 example 142 (PT 4274) R2 layer R1 layer Polyolefin resinPolyolefin resin Weight Number of percentage Melting Volume grains withof group temp. of percentage diameter of derived R1 layer of grains 0.1to 5 μm in from Resin resin at with diameter cube with one Filmcarboxylic layer extrusion Sample of 0.1 to 5 μm side of 10 μm thicknessResin acid Tg thickness laminating film (vol %) (grains) (μm) type (wt%) (° C.) (μm) time (° C.) Inventive 14 2500 22 EM1 21 <−30 4 260example 123 Inventive 14 2500 22 EM2 18 <−30 4 260 example 124 Inventive14 2500 22 EM4 8 <−30 4 260 example 125 Inventive 14 2500 22 EM5 7 <−304 260 example 126 Inventive 14 2500 22 EM7 1 <−30 4 260 example 127Inventive 14 2500 22 EM8 6 20 4 260 example 128 Inventive 14 2500 22 EM65 <−30 4 260 example 129 Inventive 14 2500 22 EM6 5 <−30 4 260 example130 Inventive 14 2500 22 EM6 5 <−30 4 260 example 131 Inventive 14 250022 EM6 5 <−30 4 260 example 132 Inventive 14 2500 22 EM6 5 <−30 4 260example 133 Inventive 14 2500 22 EM6 5 <−30 4 260 example 134 Inventive14 2500 22 EM6 5 <−30 4 260 example 135 Inventive 14 2500 22 EM6 5 <−304 260 example 136 Inventive 17 2500 25 EM6 5 <−30 3 285 example 137Inventive 14 2500 22 EM6 5 <−30 4 260 example 138 Inventive 14 2500 22EM6 5 <−30 4 260 example 139 Inventive 14 2500 22 EM6 5 <−30 4 260example 140 Inventive 14 2500 22 EM6 5 <−30 4 260 example 141 Inventive17 2500 25 EM6 5 <−30 3 285 example 142 *2) Silicone of lubricant isadded by 3 weight part to 100 weight part of mixed resin. *3)Tetrakis-[methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane offree radical inhibitor is added by 0.1 weight part to 100 weight part ofmixed resin. *4) Bond First 20B (manufactured by Sumitomo Chemical Co.,Ltd.) of compatibilizing agent is added by 3 weight part to 100 weightpart of mixed resin.

TABLE 34 R1 layer Polyolefin resin Weight R0 layer Polyester percentageResin resin of group Blending Polyester layer Melting derived from ratioin Sample resin thickness Resin point Resin carboxylic Tg entire filmtype (μm) type (° C.) Additive type acid (wt %) (° C.) resin (wt %)Comparative PET 255 None None — — 0 example 39 Comparative PET/ 235 NoneNone — — 0 example 40 PBT Comparative PET/ 220 None None — — 0 example41 AD Comparative PET/I 230 None None — — 0 example 42 Comparative PET/I230 None EPR 0 <−30 15 example 43 Comparative PET/I 230 None EM3 11 <−302 example 44 Comparative PET/I 230 None EM3 11 <−30 2 example 45Comparative PET/I 230 None EM3 11 <−30 35 example 46 Comparative PET/I230 None EM3 11 <−30 35 example 47 Comparative PET/I 230 None EM4 8 <−3015 example 48 Comparative PET 255 None 15 <−30 15 example 49 (PT 4274)Comparative PET/I 230 None EM4 8 <−30 15 example 143 Comparative PET/I230 None EM4 8 <−30 15 example 144 Comparative PET 4 PET/I 230 None EM48 <−30 15 example 50 Comparative PET 4 PET 255 None 15 <−30 15 example51 (PT 4274) Inventive PET 4 PET/I 230 None EM4 8 <−30 15 example 145Inventive PET 4 PET/I 230 None EM4 8 <−30 15 example 146 R2 layer R1layer Polyolefin resin Polyolefin resin Weight Number of percentageMelting Volume grains with of group temp. of percentage diameter ofderived R1 layer of grains 0.1 to 5 μm in from Resin resin at withdiameter cube with one Film carboxylic layer extrusion Sample of 0.1 to5 μm side of 10 μm thickness Resin acid Tg thickness laminating film(vol %) (grains) (μm) type (wt %) (° C.) (μm) time (° C.) Comparative 00 22 EM6 5 <−30 4 285 example 39 Comparative 0 0 22 EM6 5 <−30 4 265example 40 Comparative 0 0 22 EM6 5 <−30 4 250 example 41 Comparative 00 22 EM6 5 <−30 4 260 example 42 Comparative 1 4 22 EM6 5 <−30 4 260example 43 Comparative 3 5 22 EM6 5 <−30 4 260 example 44 Comparative 350 22 EM6 5 <−30 4 260 example 45 Comparative 30 20000 22 EM6 5 <−30 4260 example 46 Comparative 30 135000 22 EM6 5 <−30 4 260 example 47Comparative 15 2500 22 None — — — 260 example 48 Comparative 17 2500 25None — — — 285 example 49 Comparative 15 2500 10 EM6 5 <−30 12  260example 143 Comparative 15 2500 32 EM6 5 <−30 3 260 example 144Comparative 15 2500 22 None — — — 260 example 50 Comparative 17 2500 25None — — — 285 example 51 Inventive 15 2500 10 EM6 5 <−30 12  260example 145 Inventive 15 2500 32 EM6 5 <−30 3 260 example 146

TABLE 35 Entire resin layer Thickness Investigation result ratioThin-wall of R1 deep drawn can Total layer Impact Impact resin to R2Pigment resistance resistance Adhesion Sample thickness layer Content(room (low after film (μm) R1/R2 Type (wt %) *1) Formability temp.)temp.) forming Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 98 Invention 265.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 99 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 100 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 101 Invention 265.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 102 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 103 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 104 Invention 265.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 105 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 106 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 107 Invention 265.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 108 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 109 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 110 Invention 265.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 111 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 112 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 113 Invention 265.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 114 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 115 Invention 11 10.0 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 116 Invention 185.0 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 117 Invention 23 6.7 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 118 Invention 30 2.0 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 119 Invention 288.3 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 120 Invention 40 7.0 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 121 Invention 46 6.7 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 122 Investigationresult Thin-wall Drawn and ironed can (DI can) deep drawn can ImpactAdhesion resistance Impact Adhesion Adhesion Flavor Sample after Flavor(room resistance after after Prop- film heating property Formabilitytemp.) (low temp.) forming heating erty Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚example 98 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 99 Invention ⊚⊚ ⊚⊚ ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 100 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 101Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 102 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 103 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 104 Invention ⊚⊚⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 105 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example106 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 107 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ example 108 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 109Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 110 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 111 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 112 Invention ⊚⊚⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 113 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example114 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 115 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ example 116 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 117Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 118 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 119 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 120 Invention ⊚⊚⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 121 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example122

TABLE 36 Entire resin layer Thickness Investigation result ratioThin-wall of R1 deep drawn can Total layer Impact Impact resin to R2Pigment resistance resistance Adhesion Sample thickness layer Content(room (low after film (μm) R1/R2 Type (wt %) *1) Formability temp.)temp.) forming Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 123 Invention26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 124 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 125 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 126 Invention 265.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 127 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 128 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 129 Invention 265.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 130 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 131 Invention 26 5.5 TiO₂ 3 ⊚ ⊚ ⊚⊚⊚ ⊚ example 132 Invention 265.5 TiO₂ 7 ⊚ ⊚ ⊚⊚⊚ ⊚ example 133 Invention 26 5.5 TiO₂ 15 ⊚ ⊚ ⊚⊚⊚ ⊚example 134 Invention 26 5.5 TiO₂ 30 ⊚ ⊚ ⊚⊚⊚ ⊚ example 135 Invention 265.5 TiO₂ 50 ⊚ ⊚ ⊚⊚⊚ ⊚ example 136 Invention 28 8.3 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 137 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 138 Invention 265.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 139 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚example 140 Invention 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 141 Invention 288.3 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 142 Investigation result Thin-wall Drawnand ironed can (DI can) deep drawn can Impact Adhesion resistance ImpactAdhesion Adhesion Flavor Sample after Flavor (room resistance afterafter Prop- film heating property Formability temp.) (low temp.) formingheating erty Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 123 Invention ⊚⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 124 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 125Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 126 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 127 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 128 Invention ⊚⊚⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 129 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example130 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 131 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ example 132 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 133Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 134 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚⊚⊚ example 135 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 136 Invention ⊚⊚⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 137 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example138 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 139 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚⊚ ⊚⊚ ⊚⊚ example 140 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 141Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 142 *1) Pigment content meansweight percentage (wt %) of pigment with respect to total film amount ofentire resin and pigment. Pigment is added to R1 layer.

TABLE 37 Entire resin layer Thickness Investigation result ratioThin-wall of R1 deep drawn can Total layer Impact Impact resin to R2Pigment resistance resistance Adhesion Sample thickness layer Content(room (low after film (μm) R1/R2 Type (wt %) *1) Formability temp.)temp.) forming Comparative 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 39Comparative 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 40 Comparative 26 5.5 None 0⊚ ⊚ ⊚⊚⊚ ⊚ example 41 Comparative 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 42Comparative 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 43 Comparative 26 5.5 None 0⊚ ⊚ ⊚⊚⊚ ⊚ example 44 Comparative 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 45Comparative 26 5.5 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 46 Comparative 26 5.5 None 0⊚ ⊚ ⊚⊚⊚ ⊚ example 47 Comparative — — None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 48Comparative — — None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 49 Invention 22 0.8 None 0 ⊚ ⊚⊚⊚⊚ ⊚ example 143 Invention 35 10.7  None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 144Comparative — — None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 50 Comparative — — None 0 ⊚ ⊚⊚⊚⊚ ⊚ example 51 Invention 22 0.8 None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 145 Invention35 10.7  None 0 ⊚ ⊚ ⊚⊚⊚ ⊚ example 146 Investigation result Thin-wallDrawn and ironed can (DI can) deep drawn can Impact Adhesion resistanceImpact Adhesion Adhesion Flavor Sample after Flavor (room resistanceafter after Prop- film heating property Formability temp.) (low temp.)forming heating erty Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 39Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 40 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ example 41 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 42Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 43 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ example 44 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 45Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 46 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ example 47 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 48Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 49 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ example 143 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 144Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 50 Comparative ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚⊚⊚ ⊚⊚ example 51 Invention ⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 145 Invention⊚⊚ ⊚⊚ ⊚ ⊚ ⊚⊚⊚ ⊚ ⊚⊚ ⊚⊚ example 146 *1) Pigment content means weightpercentage (wt %) of pigment with respect to total film amount of entireresin and pigment. Pigment is added to R1 layer.

1. A resin film of a two-layer construction comprising: (a) a resinlayer R1 comprising a non-stretched resin film which consistsessentially of a thermoplastic polyester resin containing 3 to 30percent by weight in a weight fraction in the entire resin of a granularresin with a grain diameter of 0.1 to 5 μm, said granular resin is amodified polyolefin resin containing 2 to 20 percent by weight of afunctional group, said functional group being a functional groupselected from the group consisting of a carboxylic acid group and acarboxylic acid ester group, and (b) a polyester resin layer R0containing at least one of polyethylene terephthalate and isophthalicacid copolymerized polyethylene terephthalate, as a basic skeleton,wherein the resin layer R1 and the resin layer R0 are laminated to eachother.
 2. The resin film according to claim 1, wherein the resin layerR1 has a thickness of 10 to 50 μm; the resin layer R0 has a thickness of1 to 10 μm; and a thickness ratio of the resin layer R1 to the resinlayer R0 is 2 to
 10. 3. The resin film according to claim 1, whichfurther comprises 5 to 40 percent by weight of a pigment.
 4. The resinfilm according to claim 1, wherein said thermoplastic polyester resin isa polyester containing at least one of a polyethylene terephthalate andisophthalic acid copolymerized polyethylene terephthalate, as a basicskeleton.
 5. The resin film according to claim 1, wherein thethermoplastic resin contains terephthalic acid and isophthalic acid,which are dicarboxylic acid components constituting the thermoplasticpolyester resin, in a molar ratio of 97/3 to 85/15.
 6. The resin filmaccording to claim 1, wherein the resin layer R1 has a thickness of 15to 25 μm and the resin layer R0 has a thickness of 3 to 5 μm.
 7. Theresin film according to claim 6, wherein the resin layer R0 has anintrinsic viscosity of 0.5 to 1.0 dl/g.
 8. The resin film according toclaim 1, wherein the resin layer R0 has an intrinsic viscosity of 0.3 to2.0 dl/g.
 9. A resin laminated metal sheet comprising a metal sheet anda resin, wherein at least one surface of the metal sheet is coated withthe resin film as set forth in claim 1, so that the resin layer R1 is incontact with the metal sheet.
 10. The resin laminated metal sheetaccording to claim 9, wherein a plane orientation coefficient in adirection parallel to a film surface of the resin film is lower than0.010.
 11. The resin laminated metal sheet according to claim 9, whereinthe resin film is formed by extruding two types of resins comprising theresin layer R1 and the resin layer R0, simultaneously from one T diedirectly on a surface of the metal sheet.
 12. The resin laminated metalsheet according to claim 9, wherein the metal sheet comprises iron. 13.A method for manufacturing a resin laminated metal sheet comprisingheating a resin constituting the resin layer R1 as set forth in claim 1,and a resin constituting the resin layer R0 as set forth in claim 1, toa temperature in a range of the melting point of the thermoplasticpolyester resin of the resin layer R1 plus 10° C. to said melting pointplus 50° C. to melt both resin layer R0 and resin layer R1 to form twomelted resins, and extrusion laminating the two melted resins in twolayers on a surface of a metal sheet.
 14. The manufacturing method for aresin laminated metal sheet according to claim 13, wherein the resinconstituting the resin layer R1 as set forth in claim 1 and the resinconstituting the resin layer R0 as set forth in claim 1 are insertedinto separate extruding machines and are melted.
 15. The resin filmaccording to claim 1, wherein said functional group is a carboxylic acidgroup.
 16. The resin film according to claim 1, wherein said functionalgroup is a carboxylic acid ester group.
 17. The resin film according toclaim 1, wherein said modified polyolefin resin is a carboxylic acidmodified polyolefin obtained by copolymerization, graft polymerizationor block polymerization of a monomer containing a carboxylic acid groupor a carboxylic acid ester group.
 18. The resin film according to claim17, wherein said monomer is selected from the group consisting ofacrylic acid, methacrylic acid, vinyl acetate, vinyl propionate, maleicacid, maleic anhydride, itaconic acid, and an unsaturated carboxylicacid with 3 to 8 carbon atoms.
 19. The resin film according to claim 17,wherein said monomer is monomethylester maleate.
 20. The resin filmaccording to claim 17, wherein said monomer is selected from the groupconsisting of methyl acrylate, methyl methacrylate, ethyl acrylate,ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isobutylacrylate, isobutyl methacrylate, n-butyl acrylate, n-butyl methacrylate,2-hydroxyethyl carboxylate, 2-hydroxyethyl methacrylate, monomethylestermaleate, glycidyl acrylate, glycidyl methacrylate, vinyl acetate,acrylamine and acrylamide.
 21. A method for manufacturing a resin filmcomprising: (a) inserting a thermoplastic polyester resin containing 3to 30 percent by weight in a weight fraction in the entire resin of agranular resin with a grain diameter of 0.1 to 5 μm, said granular resinis a modified polyolefin resin containing 2 to 20 percent by weight of afunctional group, said functional group being a functional groupselected from the group consisting of a carboxylic acid group and acarboxylic acid ester group in an extruding machine as a raw materialresin to melt the resin and form a molten resin, (b) inserting apolyester resin layer R0 containing at least one of polyethyleneterephthalate and isophthalic acid copolymerized polyethyleneterephthalate, as a basic skeleton, in an extruding machine to melt thepolyester resin and form a molten polyester resin, and (c) forming afilm comprising a two-layer construction by extruding the molten resinand the molten polyester resin from one T die.